Estimating source regions of European emissions of trace gases from observations at Mace Head

A technique is described for identifying probable source locations for a range of greenhouse and ozone-depleting trace gases from the long-term measurements made at Mace Head, Ireland. The Met. Office's dispersion model NAME is used to predict concentrations at Mace Head from all possible sources in Europe, then source regions identified as those which consistently lead to elevated concentrations at Mace Head. Estimates of European emissions and their distribution are presented for a number of trace gases for the period 1995–1998. Estimated emission patterns are realistic, given the nature and varied applications of the species considered. The results indicate that whilst there are limitations, useful information about source distribution can be extracted from continuous measurements at a remote site. It is probable that much improved estimates could be derived if observations were available from a number of sites. The ability to assess emissions has obvious implications in monitoring compliance with internationally agreed quota and protocols.     

International field intercomparison measurements of atmospheric mercury species at Mace Head,Ireland

Eleven laboratories from North America and Europe met at Mace Head, Ireland for the period 11–15 September 1995 for the first international field intercomparison of measurement techniques for atmospheric mercury species in ambient air and precipitation at a marine background location. Different manual methods for the sampling and analysis of total gaseous mercury (TGM) on gold and silver traps were compared with each other and with new automated analyzers. Additionally, particulate-phase mercury (Hg_part) in ambient air, total mercury, reactive mercury and methylmercury in precipitation were analyzed by some of the participating laboratories. Whereas measured concentrations of TGM and of total mercury in precipitation show good agreement between the participating laboratories, results for airborne particulate-phase mercury show much higher differences. Two laboratories measured inorganic oxidized gaseous mercury species (IOGM), and obtained levels in the low picogram m^-3 range.     

The phase-in and phase-out of European emissions of HCFC-141b and HCFC-142b under the Montreal Protocol: Evidence from observations at Mace Head,Ireland and Jungfraujoch,Switzerland from 1994 to 2004

The mixing ratios of HCFC-141b (1,1-dichlorofluoroethane) and HCFC-142b (1-chloro-1,1-difluoroethane) have been rising steadily in baseline air at Mace Head, Ireland over the 10-year period from 1994 to 2004. These HCFCs are widely used replacements for the chlorofluorocarbons phased out under the Montreal Protocol and its subsequent amendments. Analysis of the HCFC content of regionally-polluted air arriving at Mace Head from the European continent shows that European emissions reached a peak during 2000–2001 and have declined subsequently, following the phase-out in their usage. European emissions of HCFC-141b have been further constrained by observations at the High-Alpine Jungfraujoch site. The reductions are consistent with the phase-out of HCFC production and use from the year 2001 onwards mandated by European regulations designed to exceed the requirements of the Montreal Protocol.     

Bioaccumulation of per- and polyfluorinated alkyl substances (PFAS) in selected species from the Barents Sea food web

The present study reports concentrations and biomagnification potential of per- and polyfluorinated alkyl substances (PFAS) in species from the Barents Sea food web. The examined species included sea ice amphipod (Gammarus wilkitzkii), polar cod (Boreogadus saida), black guillemot (Cepphus grylle) and glaucous gull (Larus hyperboreus). These were analyzed for PFAS, polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs) and polybrominated diphenyl ethers (PBDEs). Perfluorooctane sulfonate (PFOS) was the predominant of the detected PFAS. Trophic levels and food web transfer of PFAS were determined using stable nitrogen isotopes (delta(15)N). No correlation was found between PFOS concentrations and trophic level within species. However, a non-linear relationship was established when the entire food web was analyzed. Biomagnification factors displayed values >1 for perfluorohexane sulfonate (PFHxS), perfluorononanoic acid (PFNA), PFOS and SigmaPFAS(7). Multivariate analyses showed that the degree of trophic transfer of PFAS is similar to that of PCB, DDT and PBDE, despite their accumulation through different pathways.     

The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.     

Role of organic and black carbon in the chemical composition of atmospheric aerosol at European background sites

The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch, Switzerland (high-alpine, PM_2.5 aerosol); (ii) K-puszta, Hungary (rural, PM_1.0 aerosol); (iii) Mace Head, Ireland (marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about 60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass. These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical) might be significant.     

An analysis of condensation nuclei levels at Mace Head,Ireland

Condensation nuclei (CN) concentrations measured at Mace Head between 1990 and 1992 are presented. The background CN concentration was found to typically range from 100 to 700 cm^-3. Concentration values were in this range for 55% of the measurement period. No seasonal cycle was observed in the CN concentration values. Concurrent equivalent black carbon (EBC) measurements are used to examine anthropogenic influences on the background CN concentration. Evidence that transatlantic air mass transport influenced the background CN concentration, contributing to increased CN and EBC levels, is shown. During polluted conditions the CN concentration was generally higher than 1000 cm^-3. The principal source for high pollution levels was European air masses arriving at the site. Very high CN concentrations, greater than 50 000 cm^-3, are attributed to local gas-to-particle conversion processes. The characteristics of a number of particle production events are considered. These show that these events are highly photochemical and occur during both clean and polluted conditions. Such production events though infrequent contributed significantly to the total aerosol number concentration.     

Black carbon aerosol and carbon monoxide in European regionally polluted air masses at Mace Head, Ireland during 1995–1998

Continuous measurements of black carbon aerosol (BCA) at the Mace Head Atmospheric Research Station on the Atlantic Ocean coast of Ireland show the occurrence of dramatically elevated concentrations when regionally polluted air masses are advected to the station. These occurrences correlate well with similar elevations in carbon monoxide and a wide range of other trace gases monitored near-simultaneously with the BCA. Using daily sector allocation and a sophisticated Lagrangian dispersion model, two independent estimates of the European emission source strength of BCA that are required to explain the Mace Head observations have been made. The best estimates of the UK and European emission source strengths of BCA are 46±14 and [(482–511)±140]×10³ tonnes yr⁻¹, respectively, and these estimates compare favourably with published inventories, at least to within ±25%, though they are considerably smaller than the emissions employed in some early global climate model studies.     

Sources and source variations for aerosol at Mace Head,Ireland

The sources and source variations for aerosol at Mace Head, Ireland, were studied by applying positive matrix factorization (PMF), a variant of factor analysis, to a 5-yr data set for bulk aerosol. Signals for the following six sources were evident year round: (1) mineral dust, (2) sea salt, (3) general pollution, (4) a secondary SO₄²⁻–Se signal that is composed of both natural (marine) and pollution (coal) components, (5) ferrous industries, (6) and a second marine (possibly biogenic) source. Analyses of seasonally stratified data suggested additional sources for iodine and oil emissions but these were present only in certain seasons, respectively. The marine signal is particularly strong in winter. The main pollution transport from Europe to Mace Head occurs in May, but the influence of continental European emissions is evident throughout the year. Mineral aerosol evidently follows a transport pathway similar to that of pollution aerosol, i.e., recirculation via the westerlies brings pollutants mixed with dust to the site from nearby land, i.e., Ireland, the United Kingdom, and the Belgium, Netherlands, and Luxemburg (Benelux) region, with some inputs from Scandinavia, Western Europe, Eastern Europe, and even the Mediterranean region. Compared with Bermuda, aerosol at Mace Head has stronger marine sources (especially marine-derived secondary SO₄²⁻ and Se) but weaker crustal and oil signals. Transport across the North Atlantic, especially in winter, cannot be ruled out.     

Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging

Introduction  

In this study, we explore the identity of a range of polyfluorinated surfactants (PFS) used for food contact materials, primarily to impart oil and water repellency on paper and board. PFS are of interest, as they can be precursors of poly- and perfluorinated alkyl substances (PFAS), of which several are persistent and are found worldwide in human blood and in the environment.     

Diurnal cycles of short-lived tropospheric alkenes at a north Atlantic coastal site

Observation of diurnal cycles in atmospheric concentrations of reactive alkenes are reported from measurements performed at a North Atlantic coastal site (Mace Head, Eire 53°19′34″N; 9°54′14″W). Species seen to exhibit distinct cycles included isoprene, ethene, propene, 1-butene, iso-butene and a substituted C₆ alkene. Five hundred and thirty air mass classified measurements were performed over a 4 week period at approximately hourly frequency and demonstrate that during periods when air flow resulted from unpolluted oceanic regions a clear daily cycle in concentrations existed, peaking at around solar noon for all species. These observations support the proposed mechanism of production via photochemical degradation of organic carbon in sea water. The observed concentrations showed strong correlation (propene R²>0.75) with solar flux, with little relationship to other meteorological or chemical parameters. The species’ short atmospheric lifetimes indicate that the source of emission was from local coastal waters within close proximity of the sampling site. At solar noon concentrations of reactive alkenes from oceanic sources were responsible for up to 88% of non-methane hydrocarbon reaction with the hydroxyl radical at this coastal marine site.     

Survey of polyfluorinated chemicals (PFCs) in the atmosphere over the northeast Atlantic Ocean

High volume air sampling in Bermuda, Sable Island (Nova Scotia) and along a cruise track from the Gulf of Mexico to northeast coast of the USA, was carried out to assess air concentrations, particle-gas partitioning and transport of polyfluorinated chemicals (PFCs) in this region. Samples were collected in the summer of 2007. Targeted compounds included the neutral PFCs: fluorotelomer alcohols (FTOHs), perfluoroalkyl sulfonamides (FOSAs) and perfluoroalkyl sulfonamido ethanols (FOSEs).Among the FTOHs, 8:2 FTOH was dominant in all samples. Sum of the concentration of FTOHs (gas+particle phase) were higher in Bermuda (mean, 34 pg m^?3) compared to Sable Island (mean, 16 pg m^?3). In cruise samples, sum of FTOHs were highly variable (mean, 81 pg m^?3) reflecting contributions from land-based sources in the northeast USA with concentrations reaching as high as 156 pg m^?3.Among the FOSAs and FOSEs, MeFOSE was dominant in all samples. In Bermuda, levels of MeFOSE were exceptionally high (mean, 62 pg m^?3), exceeding the FTOHs. Sable Island samples also exhibited the dominance of MeFOSE but at a lower concentration (mean, 15 pg m^?3). MeFOSE air concentrations (pg m^?3) in cruise samples ranged from 1.6 to 73 and were not linked to land-based sources. In fact high concentrations of MeFOSE observed in Bermuda were associated with air masses that originated over the Atlantic Ocean.The partitioning to particles for 8:2 FTOH, 10:2 FTOH, MeFOSE and EtFOSE ranged from as high as 15 to 42% for cruise samples to 0.9 to 14% in Bermuda. This study provides key information for validating and developing partitioning and transport models for the PFCs.     

Determination of pentachlorophenol (PCP) in waste wood--method comparison by a collaborative trial

Two independently developed and validated procedures for the determination of pentachlorophenol (PCP) in waste wood were compared by means of a collaborative trial. Both methods foresee quantification of PCP by gas chromatography (GC-ECD) after acetylation and differ with regard to the use of methanol or toluene/sulphuric acid, respectively, as solvent in the sonication extraction step. Test samples with established analyte homogeneity were prepared from a ground "real life" starting material. A total of 23 participating laboratories with experience in wood preservative analysis were instructed to apply both methods to three levels of content in the range of 0.5-20 mg PCP/kg. In case of the toluene/sulphuric acid extraction, lower recoveries and higher interlaboratory dispersion of results at the higher PCP contents were observed. Seen against the background of the Horwitz equation a reproducibility standard deviation of approximately 19% for the methanol extraction at the 4.5 mg/kg level meets the requirement for a sound analytical method. Thus, the sonication extraction procedure with methanol has been annexed as a reference method to the German waste wood regulation.     

Volcanic sulphate and arctic dust plumes over the North Atlantic Ocean

High time resolution aerosol mass spectrometry measurements were conducted during a field campaign at Mace Head Research Station, Ireland, in June 2007. Observations on one particular day of the campaign clearly indicated advection of aerosol from volcanoes and desert plains in Iceland which could be traced with NOAA Hysplit air mass back trajectories and satellite images. In conjunction with this event, elevated levels of sulphate and light absorbing particles were encountered at Mace Head. While sulphate concentration was continuously increasing, nitrate levels remained low indicating no significant contribution from anthropogenic pollutants. Sulphate concentration increased about 3.8 μg m⁻³ in comparison with the background conditions. Corresponding sulphur flux from volcanic emissions was estimated to about 0.3 TgS yr⁻¹, suggesting that a large amount of sulphur released from Icelandic volcanoes may be distributed over distances larger than 1000 km. Overall, our results corroborate that transport of volcanogenic sulphate and dust particles can significantly change the chemical composition, size distribution, and optical properties of aerosol over the North Atlantic Ocean and should be considered accordingly by regional climate models.     

Polyfluorinated chemicals in a spatially and temporally integrated food web in the Western Arctic

This study reports on an investigation of the presence of polyfluorinated chemicals in a spatially and temporally integrated set of biological samples representing an Arctic food web. Zooplankton, Arctic cod, and seal tissues from the western Canadian Arctic were analyzed for perfluoroalkyl sulfonates [PFAS], perfluorocarboxylates [PFCAs], and other polyfluorinated acids. Perfluorooctane sulfonate [PFOS] was found in all samples [0.20-34 ng/g] and in the highest concentrations. PFCAs from nine to 12 carbons were quantified in most of the samples [0.28-6.9 ng/g]. PFCAs with carbon chain lengths of eight or less were not detected. Likewise, 8-2 fluorotelomer acid [8-2 FTA] and 8-2 fluorotelomer unsaturated acid [8-2 FTUA], products of fluorotelomer environmental transformation, were not detected. 2H,2H,3H,3H, heptadecafluoro decanoic acid [7-3 Acid], an additional metabolite from fluorotelomer biological transformation, was detected only in seal liver tissue [0.5-2.5 ng/g]. The ratios of branched to linear PFOS isomers in fish and seal tissue were not similar and did not match that of technical PFOS as manufactured. No branched PFCA isomers were detected in any samples. It is concluded that differing pharmacokinetics complicate the use of branched to linear ratios of PFCAs in attributing their presence to a specific manufacturing process. A statistical analysis of the data revealed significant correlations between PFOS and the PFCAs detected as well as among the PFCAs themselves. The 7-3 Acid was not correlated with either PFCAs or PFAS, which suggests that it may have a different exposure pathway.     

Methane emissions from peat bogs in the vicinity of the Mace Head Atmospheric Research Station over a 12-year period

Methane emissions from the peat bogs in Connemara, Ireland have been inferred from the trace gas observations at the Mace Head Atmospheric Research Station using the nocturnal box method. A total of 237 local events, during April to September, over a 12-year period have been studied. Simultaneous emissions of methane, carbon dioxide and chloroform are routinely observed under nocturnal inversions with low wind speeds from the peat bogs proximal to Mace Head. Night-time deposition of ozone and hydrogen occurs concurrently with these emissions. Using the temporally correlated methane and ozone data we estimate methane emissions from each event. Simultaneous methane and chloroform emissions, together with ozone and hydrogen deposition have been characterised, leading to the estimation of methane emission rates for each event. The mean methane emission flux was found to be 400 ± 90 ng m^?2 s^?1. A strong seasonal cycle was found in the methane emission fluxes but there was little evidence of a long-term trend in the emissions from the peat bogs in the vicinity of the Mace Head station.     

Continuous observations of carbon dioxide at Mace Head,Ireland from 1995 to 1999 and its net European ecosystem exchange

A 5-yr record of continuous high-frequency carbon dioxide CO₂ observations over the 1995–1999 period for the Mace Head Atmospheric Research Station has been examined to reveal a complex interplay between local- and regional-scale sources and sinks. During the winter months, an additional CO₂ source, over and above fossil fuel combustion, is required to support the observed concentrations of CO₂ in European regionally polluted air masses. During the summer months, an additional CO₂ sink is required. Over the entire study period, the additional net European ecosystem exchange source–sink required is –0.36±0.4 Gtonne C yr⁻¹.     

Distribution and sources of polyfluoroalkyl substances (PFAS) in the River Rhine watershed

The concentration profile of 40 polyfluoroalkyl substances (PFAS) in surface water along the River Rhine watershed from the Lake Constance to the North Sea was investigated. The aim of the study was to investigate the influence of point as well as diffuse sources, to estimate fluxes of PFAS into the North Sea and to identify replacement compounds of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In addition, an interlaboratory comparison of the method performance was conducted. The PFAS pattern was dominated by perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) with concentrations up to 181 ng/L and 335 ng/L, respectively, which originated from industrial point sources. Fluxes of ΣPFAS were estimated to be ∼6 tonnes/year which is much higher than previous estimations. Both, the River Rhine and the River Scheldt, seem to act as important sources of PFAS into the North Sea.     

Comparisons of coarse-mode aerosol nitrate and ammonium at two polluted coastal sites

Direct atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters and can be enhanced by heterogeneous reactions between gaseous atmospheric nitrogen species and aerosol sea salt, which increase deposition rates. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland. Major-ion aerosol concentrations were determined and temporal patterns were interpreted with the use of air-mass back trajectories. Low levels of terrestrially derived material were seen during periods of clean, onshore flow, with respective concentration ranges for nitrate and ammonium of 0.47–220 and below detection limit to 340 nmol m⁻³. Corresponding levels of marine derived material during these periods were high, with sodium concentrations ranging from 39 to 1400 nmol m⁻³. Highest levels of terrestrially derived material were seen during polluted, offshore flow, where the air had passed recently over strong source regions of the UK and northern Europe, with concentration ranges of nitrate and ammonium of 5.6–790 and 9.7–1000 nmol m⁻³, respectively. During polluted flow ∼40–60% of the nitrate was found in the coarse mode (>1 μm diameter) and under clean marine conditions almost 100% conversion was seen. In addition, our data suggests strong evidence for dissolution/coagulation processes that also shift nitrate to the coarse mode. Furthermore, such processes are thought also to give rise to the size-shifting of aerosol ammonium, since significant coarse-mode fractions of this species (∼19–45%) were seen at both sites. A comparison of the relative importance of nitrate and ammonium in the overall dry deposition of inorganic fixed-nitrogen at each site indicates that at Weybourne the mass-weighted dry deposition velocity of the latter is around double that seen at Mace Head with its resultant contribution to the overall inorganic nitrogen dry flux exceeding that of nitrate.     

Improved and Standardized Methodology for Oil Spill Fingerprinting

The existing Nordtest methodology for oil spill Identification has over the past 10 years formed an important "platform" for solving oil spill identification cases both in the Scandinavian countries as well as other countries in Europe, the USA and Canada. " Revision of the Nordtest Methodology for Oil Spill Identification " is a cooperative project between the National Oil Spill Identification laboratories in Norway, Sweden, Finland, Denmark and the Battelle Memorial Institute (Duxbury) in the USA. The goals of the project are: (1) to refine the existing Nordtest methodology into a technically more robust and defensible oil spill identification methodology with focus on determination of quantitative diagnostic indices (ratios) and (2) to adjust the revised Nordtest methodology into guidelines for the European Committee for Standardization (CEN). This paper presents the recommended methodology for the analytical oil spill identification part. The sampling techniques and handling of oil samples and background (reference) samples prior to their arrival at the environmental forensic laboratory is not covered in this paper. The recommended methodology approach is a result of documented analytical improvements and a more quantitative treatment of analytical data from gas chromatographic-flame ionization detector (GC/FID) and gas chromatographic-mass spectrometer methods (GC/MS-SIM) and the operational experiences over past few years among the participating forensic laboratories. The experience and literature in the field of oil exploration and production geochemistry have also played an important role for the recommended methodology. The results from a recent Round Robin test carried out among 12 laboratories using this new methodology are presented in a separate paper in this issue (Faksness et at ., 2002d).