Field evaluation and calibration of a small axial passive air sampler for gaseous and particle bound polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated analogues (OPAHs) are ubiquitous air pollutants known to cause adverse health effects. PAH air levels are commonly monitored by active sampling but passive sampling has become popular because of its lower cost and simplicity, which facilitate long-term sampling and increased spatial coverage. However, passive samplers are less suitable for short-term sampling and are in general less accurate than active samplers because they require reliable sampling rate (Rs) measurements for individual analytes under diverse environmental conditions. In this study a small passive sampler designed to sample both particle-bound and gaseous compounds was evaluated and calibrated for PAHs and OPAHs in a traffic environment by co-deployment with active samplers for two weeks. Despite the relatively low average air concentrations of PM10 (20 µg/m(3)), PM2.5 (5 µg/m(3)), total PAHs (4.2 ng/m(3)), and OPAHs (2.3 ng/m(3)) at the site, detectable quantities (on average 24 times above blank values) of the full range of PAHs and OPAHs were captured, with low variability (average RSD of 16%). This was accomplished by using a Tenax(®) TA-modified glass fiber substrate that is compatible with highly sensitive thermal desorption GC-MS analysis, which made it possible to achieve detection limits per sample in the pg range. Experiments with inverted samplers revealed that the relative contribution of gravitational settling to the sampling of particles carrying PAHs and OPAHs was around 3.5 times larger than other deposition mechanisms. Average Rs values for individual OPAHs and PAHs were 0.046 ± 0.03 m(3)/day and 0.12 ± 0.07 m(3)/day, respectively, with no appreciable difference between the values for particle-associated and gaseous compounds. Furthermore, the Rs values were competitive with other currently used passive samplers if normalized for substrate area. Overall, the new sampler's performance, simplicity and ability to generate relatively time-resolved data make it a promising candidate for diverse SVOC monitoring studies.

A method for evaluating aerosol leakage through the interface between protective suits and full-face respirators.

Military personnel and first responders use a range of personal equipment including protective suits, gloves, boots, and respirators to prevent exposure of their skin and airways to hazardous chemical, biological, radiological, and/or nuclear substances. Although each individual item of personal protective equipment is well tested against existing standards, it is also necessary to consider the performance of the interfaces between items in terms of prevention from exposure, and the protection system as a whole. This article presents an aerosol challenge method for assessing the performance of the interface between a respirator and the hood of a protective suit. The interface is formed between the sealing strip of the hood and the surface of the respirator's outer sealing area and is affected by how well the sealing strip can cover and adapt to the sealing area. The method evaluates the leakage of particles of different sizes into the hood via the interface by particle counting at sampling points around the respirator's perimeter. Three different respirators were tested together with a single hood having a tight-fitting seal. The method variation between measurements was low but increased appreciably when the protective ensemble was re-dressed between measurements. This demonstrates the difficulty of achieving a reliable and reproducible seal between respirator and hood under normal conditions. Different leakage patterns were observed for the three respirators and were linked to some specific design features, namely the respirator's sealing area at the chin and its width at cheek level. Induced leak experiments showed that to detect substantial particle leakage, channels at the hood-respirator interface must be quite large. The method outlined herein provides a straightforward way of evaluating hood-respirator interfaces and could be useful in the further development of personal protective equipment.

Mobile decontamination units-room for improvement?

INTRODUCTION: Mobile decontamination units are intended to be used at the accident site to decontaminate persons contaminated by toxic substances. A test program was carried out to evaluate the efficacy of mobile decontamination units. OBJECTIVE: The tests included functionality, methodology, inside environment, effects of wind direction, and decontamination efficacy. METHODS: Three different types of units were tested during summer and winter conditions. Up to 15 test-persons per trial were contaminated with the imitation substances Purasolve ethyl lactate (PEL) and methyl salicylate (MES). Decontamination was carried out according to standardized procedures. During the decontamination trials, the concentrations of the substances inside the units were measured. After decontamination, substances evaporating from test-persons and blankets as well as remaining amounts in the units were measured. RESULTS: The air concentrations of PEL and MES inside the units during decontamination in some cases exceeded short-term exposure limits for most toxic industrial chemicals. This was a problem, especially during harmful wind conditions, i.e., wind blowing in the same direction as persons moving through the decontamination units. Although decontamination removed a greater part of the substances from the skin, the concentrations evaporating from some test-persons occasionally were high and potentially harmful if the substances had been toxic. The study also showed that blankets placed in the units absorbed chemicals and that the units still were contaminated five hours after the end of operations. CONCLUSIONS: After decontamination, the imitation substances still were present and evaporating from the contaminated persons, blankets, and units. These results indicate a need for improvements in technical solutions, procedures, and training.

Photochemical formation of polybrominated dibenzo-p-dioxins from environmentally abundant hydroxylated polybrominated diphenyl ethers.

High levels of polybrominated dibenzo-p-dioxins (PBDDs) have been found in Baltic Sea biota, where the toxic load owing to, for example, polychlorinated dibenzo-p-dioxins and other organic pollutants is already high. The levels and geographic pattern of PBDDs suggest biogenic rather than anthropogenic origin, and both biotic and abiotic formation pathways have been proposed. Photochemical formation from hydroxylated polybrominated diphenyl ethers (OH-PBDE) is a proposed pathway for PBDDs in marine environments. Ultraviolet radiation-initiated transformations of OH-BDEs 47, 68, 85, 90, 99, and 123, which all are abundant in the environment, were investigated. It was shown that the most abundant PBDDs in the environment (1,3,7-triBDD and 1,3,8-triBDD) can be formed from the most abundant OH-BDEs (OH-BDE 47 and OH-BDE 68) at high rates and with percentage yields. In fact, most of the PBDDs that have been identified in the Baltic Sea environment were formed with high yield from the six studied OH-PBDE, through initial cyclization and subsequent debromination reactions. The high formation yields point to this route as an important source of PBDDs in biota. However, congeners showing relatively high retention in fish, specifically 1,3,6,8- and 1,3,7,9-tetraBDD, were not formed. These are likely formed by enzymatic coupling of brominated phenols.

Formation of environmentally relevant brominated dioxins from 2,4,6,-tribromophenol via bromoperoxidase-catalyzed dimerization.

Polybrominated dibenzo-p-dioxins (PBDD) are emerging environmental pollutants with structural similarities to the highly characterized toxicants polychlorinated dibenzo-p-dioxins. The geographical and temporal variations of PBDD in biota samples from the Baltic Sea do not display features that are normally related to anthropogenic sources such as incineration, and therefore the natural formation of PBDDs has been suggested. This study of the bromoperoxidase mediated oxidative coupling of 2,4,6-tribromophenol (an abundant substance that is naturally formed in marine systems) identified the formation of ppb-level yields of 1,3,6,8-tetrabromodibenzo-p-dioxin (1,3,6,8-TeBDD) through direct condensation. Additional TeBDDs (1,3,7,9-TeBDD, 1,2,4,7-TeBDD, and/or 1,2,4,8-TeBDD) and tri-BDDs (1,3,7-TrBDD and 1,3,8-TrBDD) were frequently formed but at lower yields. The formation of these TeBDDs probably proceeds via bromine shifts or Smiles rearrangements, whereas the TrBDDs may result from subsequent debromination processes. Because all of the congeners formed by oxidative coupling and subsequent reactions are also found in Baltic Sea biota, the results support the theory that PBDDs are formed from natural precursors.

Retention and maternal transfer of environmentally relevant polybrominated dibenzo-p-dioxins and dibenzofurans, polychlorinated dibenzo-p-dioxins and dibenzofurans, and polychlorinated biphenyls in zebrafish (Danio rerio) after dietary exposure.

High levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), mono- and non-ortho-polychlorinated biphenyls (PCBs), and polybrominated dibenzo-p-dioxins (PBDDs) are found in fish from coastal areas in the Baltic Sea, which may cause ecotoxicological effects. To increase our understanding of the persistency of the emerging pollutants polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), fish feed was spiked with 21 PBDD/Fs, 17 PCDD/Fs, and 30 PCBs and fed to zebrafish (Danio rerio). Concentrations in fish and eggs were examined during a 6- or 12-week uptake period, and a 6-week elimination period. Steady-state was reached for 2-, 3-, 7-, and/or 8-substituted tri- and tetra-BDD/Fs; 2,3,7,8-tetra-BDD (2,3,7,8-TeBDD) was the most strongly retained. Steady-state was not reached for tetra- to hexa-CDDs. Non-2,3,7,8 congeners showed little or no retention. Most PCBs had high retention and did not reach steady state. Half-lives decreased in the order PCBs > PCDD/Fs > PBDD/Fs. Concentrations of 2,3,7,8-substituted penta- to octa-CDD/Fs decreased with their degree of chlorination, suggesting that the rate-limiting factor for uptake is low bioavailability. Maternal transfer was observed for all retained compounds, with most transfer factors <1, indicating that transfer rates are affected by the poor water solubility of the compounds. The limited retention of the major PBDD congeners found in Baltic Sea fish suggests that they are exposed to high or very high concentrations via either food or water.

Polybrominated and mixed brominated/chlorinated dibenzo-p-dioxins in sponge (Ephydatia fluviatilis) from the Baltic Sea.

Polybrominated dibenzo-p-dioxins (PBDDs) have recently been found in the Baltic Sea at concentrations 1000 times above that of the chlorinated analogs (PCDDs), yet their sources are undefined. Marine production of organobrominated compounds by sponges is well documented. The objective of the current study was to investigate the potential for an aquatic sponge (Ephydatia fluviatilis), common to the Baltic Sea, to produce PBDDs and other organobromine compounds in the field. Mono- to pentaBDDs as well as several mixed brominated/chlorinated dibenzo-p-dioxins (Br/Cl-DDs), PCDDs and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were quantified in sponge from the SW Baltic. Concentrations of individual PBDDs in the range 1-80 ng per g extractable organic matter were similar as in blue mussels from the Baltic Sea and about 25 000 times higher than 2,3,7,8-tetraCDD. To the best of our knowledge, this is the first time Br/Cl-DDs are reported in biota from a background environment. While this study does not point out sponges as a dominant source, the concentrations of PBDDs in sponge relative to related anthropogenic compounds such as PBDEs and PCDDs as well as the relative abundance of brominated dioxins and furans strengthens the idea of natural production.