Comparison of several wood smoke markers and source apportionment methods for wood burning particulate mass

Residential wood combustion has only recently been recognized as a major contributor to air pollution in Switzerland and in other European countries. A source apportionment method using the aethalometer light absorption parameters was applied to five winter campaigns at three sites in Switzerland: a village with high wood combustion activity in winter, an urban background site and a highway site. The particulate mass from traffic (PMtraffic) and wood burning (PMwb) emissions obtained with this model compared fairly well with results from the 14C source apportionment method. PMwb from the model was also compared to well known wood smoke markers such as anhydrosugars (levoglucosan and mannosan) and fine mode potassium, as well as to a marker recently suggested from the Aerodyne aerosol mass spectrometer (mass fragment m/z 60). Additionally the anhydrosugars were compared to the 14C results and were shown to be comparable to literature values from wood burning emission studies using different types of wood (hardwood, softwood). The levoglucosan to PMwb ratios varied much more strongly between the different campaigns (4–13%) compared to mannosan to PMwb with a range of 1–1.5%. Possible uncertainty aspects for the various methods and markers are discussed.

The role of seasonality of mineral dust concentration and size on glacial/interglacial dust changes in the EPICA Dronning Maud Land ice core

We present a record of particulate dust concentration and size distribution in subannual resolution measured on the European Project for Ice Coring in Antarctica (EPICA) Dronning Maud Land (EDML) ice core drilled in the Atlantic sector of the East Antarctic plateau. The record reaches from present day back to the penultimate glacial until 145,000 years B.P. with subannual resolution from 60,000 years B.P. to the present. Mean dust concentrations are a factor of 46 higher during the glacial (~850–4600 ng/mL) compared to the Holocene (~16–112 ng/mL) with slightly smaller dust particles during the glacial comparedto the Holocene and with an absolute minimum in the dust size at 16,000 years B.P. The changes in dust concentration are mainly attributed to changes in source conditions in southern South America. An increase in the modal value of the dust size suggests that at 16,000 years B.P. a major change in atmospheric circulation apparently allowed more direct transport of dust particles to the EDML drill site. We find a clear in-phase relation of the seasonal variation in dust mass concentration and dust size during the glacial (r(conc,size) = 0.8) but no clear phase relationship during the Holocene (0 concentration from the glacial to the Holocene.

Ground-based and airborne in-situ measurements of the Eyjafjallajökull volcanic aerosol plume in Switzerland in spring 2010

The volcanic aerosol plume resulting from the Eyjafjallajökull eruption in Iceland in April and May 2010 was detected in clear layers above Switzerland during two periods (17–19 April 2010 and 16–19 May 2010). In-situ measurements of the airborne volcanic plume were performed both within ground-based monitoring networks and with a research aircraft up to an altitude of 6000 m a.s.l. The wide range of aerosol and gas phase parameters studied at the high altitude research station Jungfraujoch (3580 m a.s.l.) allowed for an in-depth characterization of the detected volcanic aerosol. Both the data from the Jungfraujoch and the aircraft vertical profiles showed a consistent volcanic ash mode in the aerosol volume size distribution with a mean optical diameter around 3 ± 0.3 μm. These particles were found to have an average chemical composition very similar to the trachyandesite-like composition of rock samples collected near the volcano. Furthermore, chemical processing of volcanic sulfur dioxide into sulfate clearly contributed to the accumulation mode of the aerosol at the Jungfraujoch. The combination of these in-situ data and plume dispersion modeling results showed that a significant portion of the first volcanic aerosol plume reaching Switzerland on 17 April 2010 did not reach the Jungfraujoch directly, but was first dispersed and diluted in the planetary boundary layer. The maximum PM10 mass concentrations at the Jungfraujoch reached 30 μgm−3 and 70 μgm−3 (for 10-min mean values) duri ng the April and May episode, respectively. Even low-altitude monitoring stations registered up to 45 μgm−3 of volcanic ash related PM10 (Basel, Northwestern Switzerland, 18/19 April 2010). The flights with the research aircraft on 17 April 2010 showed one order of magnitude higher number concentrations over the northern Swiss plateau compared to the Jungfraujoch, and a mass concentration of 320 (200–520) μgm−3 on 18 May 2010 over the northwestern Swiss plateau. The presented data significantly contributed to the time-critical assessment of the local ash layer properties during the initial eruption phase. Furthermore, dispersion models benefited from the detailed information on the volcanic aerosol size distribution and its chemical composition.

Modeling of temperature and turbidity in a natural lake and a reservoir connected by pumped-storage operations

Pumped-storage (PS) systems are used to store electric energy as potential energy for release during peak demand. We investigate the impacts of a planned 1000 MW PS scheme connecting Lago Bianco with Lago di Poschiavo (Switzerland) on temperature and particle mass concentration in both basins. The upper (turbid) basin is a reservoir receiving large amounts of fine particles from the partially glaciated watershed, while the lower basin is a much clearer natural lake. Stratification, temperature and particle concentrations in the two basins were simulated with and without PS for four different hydrological conditions and 27 years of meteorological forcing using the software CE-QUAL-W2. The simulations showed that the PS operations lead to an increase in temperature in both basins during most of the year. The increase is most pronounced (up to 4°C) in the upper hypolimnion of the natural lake toward the end of summer stratification and is partially due to frictional losses in the penstocks, pumps and turbines. The remainder of the warming is from intense coupling to the atmosphere while water resides in the shallower upper reservoir. These impacts are most pronounced during warm and dry years, when the upper reservoir is strongly heated and the effects are least concealed by floods. The exchange of water between the two basins relocates particles from the upper reservoir to the lower lake, where they accumulate during summer in the upper hypolimnion (10 to 20 mg L−1) but also to some extent decrease light availability in the trophic surface layer.

Centennial mineral dust variability in high-resolution ice core data from Dome C, Antarctica

Ice core data from Antarctica provide detailed insights into the characteristics of past climate, atmospheric circulation, as well as changes in the aerosol load of the atmosphere. We present high-resolution records of soluble calcium (Ca2+), non-sea-salt soluble calcium (nssCa2+), and particulate mineral dust aerosol from the East Antarctic Plateau at a depth resolution of 1 cm, spanning the past 800 000 years. Despite the fact that all three parameters are largely dust-derived, the ratio of nssCa2+ to particulate dust is dependent on the particulate dust concentration itself. We used principal component analysis to extract the joint climatic signal and produce a common high-resolution record of dust flux. This new record is used to identify Antarctic warming events during the past eight glacial periods. The phasing of dust flux and CO2 changes during glacial-interglacial transitions reveals that iron fertilization of the Southern Ocean during the past nine glacial terminations was not the dominant factor in the deglacial rise of CO2 concentrations. Rapid changes in dust flux during glacial terminations and Antarctic warming events point to a rapid response of the southern westerly wind belt in the region of southern South American dust sources on changing climate conditions. The clear lead of these dust changes on temperature rise suggests that an atmospheric reorganization occurred in the Southern Hemisphere before the Southern Ocean warmed significantly.

Modeling the formation and aging of secondary organic aerosols during CalNex 2010

Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model–measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model–measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the recent parameterizations overpredict urban SOA formation at long photochemical ages (3 days) compared to observations from multiple sites, which can lead to problems in regional and especially global modeling. However, reducing IVOC emissions by one-half in the model to better match recent IVOC measurements improves SOA predictions at these long photochemical ages. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Measured polycyclic aromatic hydrocarbons (naphthalenes) contribute 0.7% of the modeled SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16–27, 35–61, and 19–35 %, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(+-3) %. The relative contribution of each source is uncertain by almost a factor of 2 depending on the parameterization used. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μgm-3 is also present due to the long-distance transport of highly aged OA, likely with a substantial contribution from regional biogenic SOA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies and which is higher on weekends. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr-1 of SOA globally, or 17% of global SOA, one third of which is likely to be non-fossil.

Study of mineral dust entrainment in the planetary boundary layer by lidar depolarisation technique

Measurements on 27 June 2011 were performed over the Southern Iberian Peninsula at Granada EARLINET station, using active and passive remote sensing and airborne and surface in-situ data in order to study the entrainment processes between aerosols in the free troposphere and those in the planetary boundary layer (PBL). To this aim the temporal evolution of the lidar depolarisation, backscatter-related Angström exponent and potential temperature profiles were used in combination with the PBL contribution to the aerosol optical depth (AOD). Our results show that the mineral dust entrainment in the PBL was caused by the convective processes which ‘trapped’ the lofted mineral dust layer, distributing the mineral dust particles within the PBL. The temporal evolution of ground-based in-situ data evidenced the impact of this process at surface level. Finally, the amount of mineral dust in the atmospheric column available to be dispersed into the PBL was estimated by means of POLIPHON (Polarizing Lidar Photometer Networking). The dust mass concentration derived from POLIPHON was compared with the coarse-mode mass concentration retrieved with airborne in-situ measurements. Comparison shows differences below 50 µg/m³ (30% relative difference) indicating a relative good agreement between both techniques.

Fine particulate matter measurements in Swiss restaurants, cafés and bars: what is the effect of spatial separation between smoking and non-smoking areas?

We performed 124 measurements of particulate matter (PM(2.5)) in 95 hospitality venues such as restaurants, bars, cafés, and a disco, which had differing smoking regulations. We evaluated the impact of spatial separation between smoking and non-smoking areas on mean PM(2.5) concentration, taking relevant characteristics of the venue, such as the type of ventilation or the presence of additional PM(2.5) sources, into account. We differentiated five smoking environments: (i) completely smoke-free location, (ii) non-smoking room spatially separated from a smoking room, (iii) non-smoking area with a smoking area located in the same room, (iv) smoking area with a non-smoking area located in the same room, and (v) smoking location which could be either a room where smoking was allowed that was spatially separated from non-smoking room or a hospitality venue without smoking restriction. In these five groups, the geometric mean PM(2.5) levels were (i) 20.4, (ii) 43.9, (iii) 71.9, (iv) 110.4, and (v) 110.3 microg/m(3), respectively. This study showed that even if non-smoking and smoking areas were spatially separated into two rooms, geometric mean PM(2.5) levels in non-smoking rooms were considerably higher than in completely smoke-free hospitality venues. PRACTICAL IMPLICATIONS: PM(2.5) levels are considerably increased in the non-smoking area if smoking is allowed anywhere in the same location. Even locating the smoking area in another room resulted in a more than doubling of the PM(2.5) levels in the non-smoking room compared with venues where smoking was not allowed at all. In practice, spatial separation of rooms where smoking is allowed does not prevent exposure to environmental tobacco smoke in nearby non-smoking areas.

Reduced muscle mass and bone size in pediatric patients with inflammatory bowel disease

BACKGROUND: Decreased bone mineral density has been reported in children with inflammatory bowel disease (IBD). We used peripheral quantitative computed tomography (pQCT) to assess bone mineralization, geometry, and muscle cross-sectional area (CSA) in pediatric IBD. METHODS: In a cross-sectional study, pQCT of the forearm was applied in 143 IBD patients (mean age 13.9 +/- 3.5 years); 29% were newly diagnosed, 98 had Crohn's disease, and 45 had ulcerative colitis. Auxological data, cumulative glucocorticoid dose, disease activity indices, laboratory markers for inflammation, and bone metabolism were related to the results of pQCT. RESULTS: Patients were compromised in height (-0.82 +/- 1.1 SD), weight (-0.77 +/- 1.0 SD), muscle mass (-1.12 +/- 1.0 SD), and total bone cross-sectional area (-0.79 +/- 1.0 SD) compared to age- and sex-matched healthy controls (z-scores). In newly diagnosed patients, the ratio of bone mineral mass per muscle CSA was higher than in those with longer disease duration (1.00 versus 0.30, P = 0.007). Serum albumin level and disease activity correlated with muscle mass, accounting for 41.0% of variability in muscle mass (P < 0.01). The trabecular bone mineral density z-score was on average at the lower normal level (-0.40 +/- 1.3 SD, P < 0.05). CONCLUSIONS: Reduced bone geometry was explained only in part by reduced height. Bone disease in children with IBD seems to be secondary to muscle wasting, which is already present at diagnosis. With longer disease duration, bone adapts to the lower muscle CSA. Serum albumin concentration is a good marker for muscle wasting and abnormal bone development.

Enantioselective determination of ondansetron and 8-hydroxyondansetron in human plasma from recovered surgery patients by liquid chromatography-tandem mass spectrometry

A liquid chromatographic-mass spectrometric assay with atmospheric pressure chemical ionization for quantification of ondansetron and its main metabolite 8-hydroxyondansetron in human plasma was presented. The enantiomeric separation was achieved on a Chiralcel OD-R column containing cellulose tris-(3,5-dimethylphenylcarbamate). The validation data were within the required limits. The assay was successfully applied to authentic plasma samples. Quantitative results from postoperative patients receiving ondansetron demonstrated a great interindividual variability in postoperative plasma drug concentrations, the metabolites were not detected in their unconjugated form. A wide variation in the S-(+)-/R-(-)-ondansetron concentration ratio between 0.14 and 7.18 is indicative for a stereoselective disposition or metabolism. In further studies CYP2D6 and CYP3A4 genotype dependent metabolism of ondansetron enantiomers as well as of co-administered drugs and clinical efficacy of the medication should be tested.

Development and validation of a liquid chromatography-tandem mass spectrometry method for the simultaneous determination of nine corticosteroid residues in bovine liver samples

A liquid chromatography tandem mass spectrometry (LC-MS/MS) confirmatory method for the simultaneous determination of nine corticosteroids in liver, including the four MRL compounds listed in Council Regulation 37/2010, was developed. After an enzymatic deconjugation and a solvent extraction of the liver tissue, the resulting solution was cleaned up through an SPE Oasis HLB cartridge. The analytes were then detected by liquid chromatography-negative-ion electrospray tandem mass spectrometry, using deuterium-labelled internal standards. The procedure was validated as a quantitative confirmatory method according to the Commission Decision 2002/657/EC criteria. The results showed that the method was suitable for statutory residue testing regarding the following performance characteristics: instrumental linearity, specificity, precision (repeatability and intra-laboratory reproducibility), recovery, decision limit (CCα), detection capability (CCβ) and ruggedness. All the corticosteroids can be detected at a concentration around 1 μg kg(-1); the recoveries were above 62% for all the analytes. Repeatability and reproducibility (within-laboratory reproducibility) for all the analytes were below 7.65% and 15.5%, respectively.

On-line SPE LC-MS/MS for the quantification of Δ9-tetrahydrocannabinol (THC) and its two major metabolites in human peripheral blood by liquid chromatography tandem mass spectrometry

A universal and robust analytical method for the determination of Δ9-tetrahydrocannabinol (THC) and two of its metabolites Δ9-(11-OH)-tetrahydrocannabinol (11-OH-THC) and 11-nor-Δ9-carboxy-tetrahydrocannabinol (THC-COOH) in human whole blood was developed and validated for use in forensic toxicology. Protein precipitation, integrated solid phase extraction and on-line enrichment followed by high-performance liquid chromatography separation and detection with a triple quadrupole mass spectrometer were combined. The linear ranges used for the three cannabinoids were from 0.5 to 20 ng/mL for THC and 11-OH-THC and from 2.5 to 100 ng/mL for THC-COOH, therefore covering the requirements for forensic use. Correlation coefficients of 0.9980 or better were achieved for all three analytes. No relevant hydrolysis was observed for THC-COOH glucuronide with this procedure--in contrast to our previous GC-MS procedure, which obviously lead to an artificial increase of the THC-COOH concentration due to the hydrolysis of the glucuronide-conjugate occurring at high pH during the phase-transfer catalyzed methylation step.

Fossil versus contemporary sources of fine elemental and organic carbonaceous particulate matter during the DAURE campaign in Northeast Spain

We present results from the international field campaign DAURE (Detn. of the sources of atm. Aerosols in Urban and Rural Environments in the Western Mediterranean), with the objective of apportioning the sources of fine carbonaceous aerosols. Submicron fine particulate matter (PM1) samples were collected during Feb.-March 2009 and July 2009 at an urban background site in Barcelona (BCN) and at a forested regional background site in Montseny (MSY). We present radiocarbon (14C) anal. for elemental and org. carbon (EC and OC) and source apportionment for these data. We combine the results with those from component anal. of aerosol mass spectrometer (AMS) measurements, and compare to levoglucosan-based ests. of biomass burning OC, source apportionment of filter data with inorg. compn. + EC + OC, submicron bulk potassium (K) concns., and gaseous acetonitrile concns. At BCN, 87 % and 91 % of the EC on av., in winter and summer, resp., had a fossil origin, whereas at MSY these fractions were 66 % and 79 %. The contribution of fossil sources to org. carbon (OC) at BCN was 40 % and 48 %, in winter and summer, resp., and 31 % and 25 % at MSY. The combination of results obtained using the 14C technique, AMS data, and the correlations between fossil OC and fossil EC imply that the fossil OC at Barcelona is ∼47 % primary whereas at MSY the fossil OC is mainly secondary (∼85 %). Day-to-day variation in total carbonaceous aerosol loading and the relative contributions of different sources predominantly depended on the meteorol. transport conditions. The estd. biogenic secondary OC at MSY only increased by ∼40 % compared to the order-of-magnitude increase obsd. for biogenic volatile org. compds. (VOCs) between winter and summer, which highlights the uncertainties in the estn. of that component. Biomass burning contributions estd. using the 14C technique ranged from similar to slightly higher than when estd. using other techniques, and the different estns. were highly or moderately correlated. Differences can be explained by the contribution of secondary org. matter (not included in the primary biomass burning source ests.), and/or by an over-estn. of the biomass burning OC contribution by the 14C technique if the estd. biomass burning EC/OC ratio used for the calcns. is too high for this region. Acetonitrile concns. correlate well with the biomass burning EC detd. by 14C. K is a noisy tracer for biomass burning. [on SciFinder(R)]

Determination of ajulemic acid and its glucuronide in human plasma by gas chromatography-mass spectrometry

A method using gas chromatography-mass spectrometry (GC-MS) and solid-phase extraction (SPE) was developed for the determination of ajulemic acid (AJA), a non-psychoactive synthetic cannabinoid with interesting therapeutic potential, in human plasma. When using two calibration graphs, the assay linearity ranged from 10 to 750 ng/ml, and 750 to 3000 ng/ml AJA. The intra- and inter-day precision (R.S.D., %), assessed across the linear ranges of the assay, was between 1.5 and 7.0, and 3.6 and 7.9, respectively. The limit of quantitation (LOQ) was 10 ng/ml. The amount of AJA glucuronide was determined by calculating the difference in the AJA concentration before ("free AJA") and after enzymatic hydrolysis ("total AJA"). The present method was used within a clinical study on 21 patients suffering from neuropathic pain with hyperalgesia and allodynia. For example, plasma levels of 599.4+/-37.2 ng/ml (mean+/-R.S.D., n=9) AJA were obtained for samples taken 2 h after the administration of an oral dose of 20 mg AJA. The mean AJA glucuronide concentration at 2h was 63.8+/-127.9 ng/ml.

The importance of growth hormone in the regulation of erythropoiesis, red cell mass, and plasma volume in adults with growth hormone deficiency

Total body water (TBW) is reduced in adult GH deficiency (GHD) largely due to a reduction of extracellular water. It is unknown whether total blood volume (TBV) contributes to the reduced extracellular water in GHD. GH and insulin-like growth factor I (IGF-I) have been demonstrated to stimulate erythropoiesis in vitro, in animal models, and in growing children. Whether GH has a regulatory effect on red cell mass (RCM) in adults is not known. We analyzed body composition by bioelectrical impedance and used standard radionuclide dilution methods to measure RCM and plasma volume (PV) along with measuring full blood count, ferritin, vitamin B12, red cell folate, IGF-I, IGF-binding protein-3, and erythropoietin in 13 adult patients with GHD as part of a 3-month, double blind, placebo-controlled trial of GH (0.036 U/kg.day). TBW and lean body mass significantly increased by 2.5 +/- 0.53 kg (mean +/- SEM; P < 0.004) and 3.4 +/- 0.73 kg (P < 0.004), respectively, and fat mass significantly decreased by 2.4 +/- 0.32 kg (P < 0.001) in the GH-treated group. The baseline RCM of all patients with GHD was lower than the predicted normal values (1635 +/- 108 vs. 1850 +/- 104 mL; P < 0.002). GH significantly increased RCM, PV, and TBV by 183 +/- 43 (P < 0.006), 350 +/- 117 (P < 0.03), and 515 +/- 109 (P < 0.004) mL, respectively. The red cell count increased by 0.36 +/- 0.116 x 10(12)/L (P < 0.03) with a decrease in ferritin levels by 39.1 +/- 4.84 micrograms/L (P < 0.001) after GH treatment. Serum IGF-I and IGF-binding protein-3 concentrations increased by 3.0 +/- 0.43 (P < 0.001) and 1.3 +/- 0.15 (P < 0.001) SD, respectively, but the erythropoietin concentration was unchanged after GH treatment. No significant changes in body composition or blood volume were recorded in the placebo group. Significant positive correlations could be established between changes in TBW and TBV, lean body mass and TBV (r = 0.78; P < 0.04 and r = 0.77; P < 0.04, respectively), and a significant negative correlation existed between changes in fat mass and changes in TBV in the GH-treated group (r = -0.95; P < 0.02). We conclude that 1) erythropoiesis is impaired in GHD; 2) GH stimulates erythropoiesis in adult GHD; and 3) GH increases PV and TBV, which may contribute to the increased exercise performance seen in these patients.