Atmospheric Transport and Deposition of Bromoanisoles Along a Temperate to Arctic Gradient.

Bromoanisoles (BAs) arise from O-methylation of bromophenols, produced by marine algae and invertebrates. BAs undergo sea-air exchange and are transported over the oceans. Here we report 2,4-DiBA and 2,4,6-TriBA in air and deposition on the Swedish west coast (Råö) and the interior of arctic Finland (Pallas). Results are discussed in perspective with previous measurements in the northern Baltic region in 2011-2013. BAs in air decreased from south to north in the order Råö > northern Baltic > Pallas. Geometric mean concentrations at Pallas increased significantly (p < 0.05) between 2002 and 2015 for 2,4-DiBA but not for 2,4,6-TriBA. The logarithm of BA partial pressures correlated significantly to reciprocal air temperature at the coastal station Råö and over the Baltic, but only weakly (2,4-DiBA) or not significantly (2,4,6-TriBA) at inland Pallas. Deposition fluxes of BAs were similar at both sites despite lower air concentrations at Pallas, due to greater precipitation scavenging at lower temperatures. Proportions of the two BAs in air and deposition were related to Henry's law partitioning and source regions. Precipitation concentrations were 10-40% of those in surface water of Bothnian Bay, northern Baltic Sea. BAs deposited in the bay catchment likely enter rivers and provide an unexpected source to northern estuaries. BAs may be precursors to higher molecular weight compounds identified by others in Swedish inland lakes.

Air-water exchange of brominated anisoles in the northern Baltic Sea.

Bromophenols produced by marine algae undergo O-methylation to form bromoanisoles (BAs), which are exchanged between water and air. BAs were determined in surface water of the northern Baltic Sea (Gulf of Bothnia, consisting of Bothnian Bay and Bothnian Sea) during 2011-2013 and on a transect of the entire Baltic in September 2013. The abundance decreased in the following order: 2,4,6-tribromoanisole (2,4,6-TBA)>2,4-dibromoanisole (2,4-DBA)≫2,6-dibromoanisole (2,6-DBA). Concentrations of 2,4-DBA and 2,4,6-TBA in September were higher in the southern than in the northern Baltic and correlated well with the higher salinity in the south. This suggests south-to-north advection and dilution with fresh riverine water enroute, and/or lower production in the north. The abundance in air over the northern Baltic also decreased in the following order: 2,4,6-TBA>2,4-DBA. However, 2,6-DBA was estimated as a lower limit due to breakthrough from polyurethane foam traps used for sampling. Water/air fugacity ratios ranged from 3.4 to 7.6 for 2,4-DBA and from 18 to 94 for 2,4,6-TBA, indicating net volatilization. Flux estimates using the two-film model suggested that volatilization removes 980-1360 kg of total BAs from Bothnian Bay (38000 km2) between May and September. The release of bromine from outgassing of BAs could be up to 4-6% of bromine fluxes from previously reported volatilization of bromomethanes and bromochloromethanes.

Spill and leakage using a drug preparation system based on double-filter technology.

Occupational exposure to cytotoxic drugs has frequently been reported during recent years. Various drug-handling systems have been applied to reduce the spill and leakage that cause this exposure. Some of these systems have also been tested for spill and leakage using independent test methods. In this paper, a new drug-handling system has been tested for spill and leakage during drug preparation. The handling system, Tevadaptortrade mark, was tested using a modification of an independent test method, the Technetium test method, based on the use of Technetium m-99 as tracer substance. The test results showed that the spill was <100 nl for all 75 preparations and was <1 nl for 70 of the preparations. This is comparable with other tested drug-handling system, e.g. isolators, PhaSealtrade mark. The test shows that the Tevadaptor drug-handling system has similar performance as drug-handling systems regarded as closed systems.

Chlorinated pesticides and natural brominated anisoles in air at three northern Baltic stations.

Polyurethane foam (PUF) disk passive samplers were deployed at one inland and two island locations in the Bothnian Bay region of the northern Baltic Sea. Uptake was linear over 81-147 d and a temperature range of -2.6 to 14.2 °C for organochlorine pesticides (OCPs) and current-use pesticides (CUPs) having log KOA ≥9 at ambient temperatures. Partial saturation of the PUF disks occurred for the more volatile OCPs hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB), and for bromoanisoles (BAs), which are products of bromophenols released by natural and anthropogenic sources. Correction for nonlinear uptake of these was made using experimentally measured PUF-air partition coefficients. Passive-derived air concentrations of pesticides were uniform over the bay and agreed within a factor of 2 or better with levels determined by active (pumped) sampling at one of the island stations. Levels of OCPs were similar to those reported at background sites in the European and Canadian Arctic and at monitoring stations in the central Baltic and southern Scandinavia, indicating long-range transport. The insecticide chlorpyrifos was 10 times lower at bay stations than in the Canadian Arctic. Insight to sources and processes was gained by examining compound profiles. Fractions Falpha = α-HCH/(α-HCH + Î³-HCH) and FTC = trans-chlordane/(trans-chlordane + cis-chlordane) at bay stations were higher than in the Norwegian and Finnish Arctic and similar to those at the southern monitoring stations. Volatilization of chlordanes from Baltic seawater may also modify FTC. Higher FTriBA = 2,4,6-TriBA/(2,4,6-TriBA + 2,4-DiBA) distinguished local volatilization from the Baltic Sea versus lower FTriBA found at the inland site and reported in air on the Norwegian coast, suggesting westerly transport from the Atlantic across Norway and Sweden.

Field estimates of polyurethane foam - air partition coefficients for hexachlorobenzene, alpha-hexachlorocyclohexane and bromoanisoles.

Partition coefficients of gaseous semivolatile organic compounds (SVOCs) between polyurethane foam (PUF) and air (KPA) are needed in the estimation of sampling rates for PUF disk passive air samplers. We determined KPA in field experiments by conducting long-term (24-48 h) air sampling to saturate PUF traps and shorter runs (2-4 h) to measure air concentrations. Sampling events were done at daily mean temperatures ranging from 1.9 to 17.5 °C. Target compounds were hexachlorobenzene (HCB), alpha-hexachlorocyclohexane (α-HCH), 2,4-dibromoanisole (2,4-DiBA) and 2,4,6-tribromoanisole (2,4,6-TriBA). KPA (mL g(-1)) was calculated from quantities on the PUF traps at saturation (ng g(-1)) divided by air concentrations (ng mL(-1)). Enthalpies of PUF-to-air transfer (ΔHPA, kJ mol(-1)) were determined from the slopes of log KPA/mL g(-1) versus 1/T(K) for HCB and the bromoanisoles, KPA of α-HCH was measured only at 14.3 to 17.5 °C and ΔHPA was not determined. Experimental log KPA/mL g(-1) at 15 °C were HCB = 7.37; α-HCH = 8.08; 2,4-DiBA = 7.26 and 2,4,6-TriBA = 7.26. Experimental log KPA/mL g(-1) were compared with predictions based on an octanol-air partition coefficient (log KOA) model (Shoeib and Harner, 2002a) and a polyparameter linear free relationship (pp-LFER) model (Kamprad and Goss, 2007) using different sets of solute parameters. Predicted KP values varied by factors of 3 to over 30, depending on the compound and the model. Such discrepancies provide incentive for experimental measurements of KPA for other SVOCs.

Sea-air exchange of bromoanisoles and methoxylated bromodiphenyl ethers in the Northern Baltic.

Halogenated natural products in biota of the Baltic Sea include bromoanisoles (BAs) and methoxylated bromodiphenyl ethers (MeO-BDEs). We identified biogenic 6-MeO-BDE47 and 2'-MeO-BDE68 in Baltic water and air for the first time using gas chromatography - high resolution mass spectrometry. Partial pressures in air were related to temperature by: log p/Pa=m/T(K)+b. We determined Henry's law constants (HLCs) of 2,4-dibromoanisole (2,4-DiBA) and 2,4,6-tribromoanisole (2,4,6-TriBA) from 5 to 30°C and revised our assessment of gas exchange in the northern Baltic. The new water/air fugacity ratios (FRs) were lower, but still indicated net volatilization in May-June for 2,4-DiBA and May - September for 2,4,6-TriBA. The net flux (negative) of BAs from Bothnian Bay (38,000km2) between May - September was revised from -1319 to -532kg. FRs of MeO-BDEs were >1, suggesting volatilization, although this is tentative due to uncertainties in their HLCs and binding to dissolved organic carbon.

Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment.

Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011-2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069-2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air-sea gas exchange and "bulk" (precipitation + dry particle) deposition, resulting in net gains of 53 and 46 kg year(-1) for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year(-1) for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.

Wipe sampling as a tool for monitoring aerosol deposition in workplaces.

As a complement to traditional exposure assessment, monitoring deposition of aerosols can be a simple and quick screening method for identifying deposited aerosols. In this presentation examples of screening studies, based on wipe sampling in combination with adequate analytical techniques, are described. These screening methods are rapid, simple and easy to carry out. The examples given in this presentation show a broad applicability and the methods are proven useful for assessing aerosol distribution in the workplace as well as to identify target spots for more extensive assessment of a worker's exposure situation.

A test method for assessment of spill and leakage from drug preparation systems.

Anti-cancer drugs are reactive compounds with known adverse health effects. To prevent occupational exposure to these drugs, there are, in most countries, regulations for handling anti-cancer drugs. Many preparation systems are available, e.g. isolators, biological safety cabinets (BSCs), filter spikes (venting spikes with micro-pore filter) and closed systems (e.g. PhaSeal). Although these systems are used, there are reports of exposure. This causes concern over how efficient these systems are to prevent spill and leakage that may cause undesired exposure when handling cytotoxic drugs. Today, this knowledge is lacking. This paper presents a method (Tc-method) for testing drug preparation systems for spill and leakage. The Tc-method is based on 99Tc(m) as a tracer, with which drug vials used for test preparations are spiked. Wipe samples are then collected around the working area to measure spill and leakage. The Tc-method has been validated using an independent method, showing good agreement between the methods. Spills down to 1 nl cm(-2) can be determined. In an appendix, the Tc-method is described in a detailed step-by-step procedure.

New approaches for assessment of occupational exposure to metals using on-site measurements.

Traditional assessment of occupational exposure to metals typically involves static or personal aerosol sampling on a membrane filter followed by a laboratory determination of the metal content on the filter sample. These techniques give results with high accuracy and low detection limits. However, they all have a drawback in that, since the samples have to be analysed in a laboratory, the results will usually be obtained days or weeks after the sampling took place. Today there is available a new generation of portable electronic micro-balances and instruments for metal analysis based on X-ray fluorescence. These instruments will make on-site measurements of metal exposure possible, which opens the way for new approaches for assessment of occupational exposure to metals. In combination with high-flow pumps, short-term sampling is possible, which allows monitoring of the exposure variation during a work shift as well as the exposure during individual work tasks of short duration. Screening measurements and emission measurements are other examples of monitoring that are facilitated using on-site determinations. Measure control monitoring can effectively be performed using on-site measurements and is an effective tool in the assessment of workplace improvements. On-site determinations can also form an effective and pedagogic tool showing workers how to perform specific tasks and demonstrating the effectiveness of different measures intended to improve their work environment. Other examples are the assessment of skin exposure using aerosol deposition on pads and screening of contamination using bulk samples.

Cisplatin contamination observed on the outside of drug vials.

Exposure to cytotoxic drugs is of great concern today. Special regulations for handling these drugs during preparation and administration have been implemented in most countries. Concern has also been raised as to whether exposure to these drugs can occur due to contaminated drug vials. In this investigation, wipe samples were taken from drug vials used for platinum-containing drugs, e.g. cisplatin and related drugs. The vials were randomly picked from unbroken packages from different manufacturers. The results showed that drug vials may already be contaminated on the outside when delivered from the manufacturer.

Sampling and analysis considerations for the determination of hexavalent chromium in workplace air.

Airborne hexavalent chromium (Cr[VI]) is a known human respiratory carcinogen and allergen. Workers in a variety of industries may be exposed to airborne hexavalent chromium, with exposures frequently occurring via inhalation and/or dermal contact. Analytical methods for the measurement of Cr(VI) compounds in workplace samples, rather than for the determination of total elemental chromium in workplace air, are often desired because exposure limit values for Cr(VI) compounds are much lower than for total Cr. For years, sampling and analytical test methods for airborne Cr(VI) have been investigated so as to provide means for occupational exposure assessment to this highly toxic species. Inter-conversion of trivalent chromium (Cr[III]) and Cr(VI) can sometimes occur during sampling and sample preparation, and efforts to minimize unwanted redox reactions involving these chromium valences have been sought. Because of differences in toxicity, there is also interest in the ability to differentiate between water-soluble and insoluble forms of Cr(VI), and procedures that provide solubility information concerning Cr(VI) compounds have been developed. This paper reviews the state of the art concerning the measurement of airborne Cr(VI) compounds in workplace aerosols and related samples.

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces.

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.

Exposure to anti-cancer drugs during preparation and administration. Investigations of an open and a closed system.

Systems for the preparation and administration of drugs are designed to ensure that the drug is not contaminated. They do not necessarily consider the work environment for the medical staff and new techniques are therefore desirable. The aim of this work is to compare a new closed system for the preparation and administration of drugs with the traditional technique with regard to airborne emission and surface spillage of drugs. Platinum, determined using adsorptive voltammetry, was used as the tracer for airborne emission. Air samples were collected during the preparation and administration, and the collected platinum on the filters was determined by adsorptive voltammetry. For determination of spills and leakage onto surfaces the radioisotope 99m-technetium was used as a tracer. The radiation from the isotope was determined on protective gloves and bench covers after preparation and administration. The mean airborne emission was 6 ng m(-3) with the closed system and 15 ng m(-3) with the traditional pump technique. The average surface spillage using the closed technique was 0.005 microL. This is significantly smaller than with the traditional technique, which resulted in an average spillage of 64 microL. Our results also show that the dominant part of the leakage is surface spillage. Inexperienced nurses could also adequately handle the closed system.