The effects of springtime mid-latitude storms on trace gas composition determined from the MACC reanalysis

The relationship between springtime air pollution transport of ozone (O3) and carbon monoxide (CO) and mid-latitude cyclones is explored for the first time using the Monitoring Atmospheric Composition and Climate (MACC) reanalysis for the period 2003–2012. In this study, the most intense spring storms (95th percentile) are selected for two regions, the North Pacific (NP) and the North Atlantic (NA). These storms (∼60 storms over each region) often track over the major emission sources of East Asia and eastern North America. By compositing the storms, the distributions of O3 and CO within a "typical" intense storm are examined. We compare the storm-centered composite to background composites of "average conditions" created by sampling the reanalysis data of the previous year to the storm locations. Mid-latitude storms are found to redistribute concentrations of O3 and CO horizontally and vertically throughout the storm. This is clearly shown to occur through two main mechanisms: (1) vertical lifting of CO-rich and O3-poor air isentropically, from near the surface to the mid- to upper-troposphere in the region of the warm conveyor belt; and (2) descent of O3-rich and CO-poor air isentropically in the vicinity of the dry intrusion, from the stratosphere toward the mid-troposphere. This can be seen in the composite storm's life cycle as the storm intensifies, with area-averaged O3 (CO) increasing (decreasing) between 200 and 500 hPa. The influence of the storm dynamics compared to the background environment on the composition within an area around the storm center at the time of maximum intensity is as follows. Area-averaged O3 at 300 hPa is enhanced by 50 and 36% and by 11 and 7.6% at 500 hPa for the NP and NA regions, respectively. In contrast, area-averaged CO at 300 hPa decreases by 12% for NP and 5.5% for NA, and area-averaged CO at 500 hPa decreases by 2.4% for NP while there is little change over the NA region. From the mid-troposphere, O3-rich air is clearly seen to be transported toward the surface, but the downward transport of CO-poor air is not discernible due to the high levels of CO in the lower troposphere. Area-averaged O3 is slightly higher at 1000 hPa (3.5 and 1.8% for the NP and NA regions, respectively). There is an increase of CO at 1000 hPa for the NP region (3.3%) relative to the background composite and a~slight decrease in area-averaged CO for the NA region at 1000 hPa (-2.7%).

Advanced source apportionment of size-resolved trace elements at multiple sites in London during winter

Trace element measurements in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 aerosol were performed with 2 h time resolution at kerbside, urban background and rural sites during the ClearfLo winter 2012 campaign in London. The environment-dependent variability of emissions was characterized using the Multilinear Engine implementation of the positive matrix factorization model, conducted on data sets comprising all three sites but segregated by size. Combining the sites enabled separation of sources with high temporal covariance but significant spatial variability. Separation of sizes improved source resolution by preventing sources occurring in only a single size fraction from having too small a contribution for the model to resolve. Anchor profiles were retrieved internally by analysing data subsets, and these profiles were used in the analyses of the complete data sets of all sites for enhanced source apportionment. A total of nine different factors were resolved (notable elements in brackets): in PM10–2.5, brake wear (Cu, Zr, Sb, Ba), other traffic-related (Fe), resuspended dust (Si, Ca), sea/road salt (Cl), aged sea salt (Na, Mg) and industrial (Cr, Ni); in PM2.5–1.0, brake wear, other traffic-related, resuspended dust, sea/road salt, aged sea salt and S-rich (S); and in PM1.0–0.3, traffic-related (Fe, Cu, Zr, Sb, Ba), resuspended dust, sea/road salt, aged sea salt, reacted Cl (Cl), S-rich and solid fuel (K, Pb). Human activities enhance the kerb-to-rural concentration gradients of coarse aged sea salt, typically considered to have a natural source, by 1.7–2.2. These site-dependent concentration differences reflect the effect of local resuspension processes in London. The anthropogenically influenced factors traffic (brake wear and other traffic-related processes), dust and sea/road salt provide further kerb-to-rural concentration enhancements by direct source emissions by a factor of 3.5–12.7. The traffic and dust factors are mainly emitted in PM10–2.5 and show strong diurnal variations with concentrations up to 4 times higher during rush hour than during night-time. Regionally influenced S-rich and solid fuel factors, occurring primarily in PM1.0–0.3, have negligible resuspension influences, and concentrations are similar throughout the day and across the regions.

Climatology and variability of trace gases in extratropical double-tropopause regions from MLS, HIRDLS, and ACE-FTS measurements

Upper tropospheric and lower stratospheric measurements from the Aura Microwave Limb Sounder (MLS), the Aura High Resolution Dynamics Limb Sounder (HIRDLS), and the Atmospheric Chemistry Experiment-Fourier transform spectrometer (ACE-FTS) are used to present the first global climatological comparison of extratropical, nonpolar trace gas distributions in double-tropopause (DT) and single-tropopause (ST) regions. Stratospheric tracers, O3, HNO3, and HCl, have lower mixing ratios ∼2–8 km above the primary (lowermost) tropopause in DT than in ST regions in all seasons, with maximum Northern Hemisphere (NH) differences near 50% in winter and 30% in summer. Southern Hemisphere winter differences are somewhat smaller, but summer differences are similar in the two hemispheres. H2O in DT regions of both hemispheres shows strong negative anomalies in November through February and positive anomalies in July through October, reflecting the strong seasonal cycle in H2O near the tropical tropopause. CO and other tropospheric tracers examined have higher DT than ST values 2–7 km above the primary tropopause, with the largest differences in winter. Large DT-ST differences extend to high NH latitudes in fall and winter, with longitudinal maxima in regions associated with enhanced wave activity and subtropical jet variations. Results for O3 and HNO3 agree closely between MLS and HIRDLS, and differences from ACE-FTS are consistent with its sparse and irregular midlatitude sampling. Consistent signatures in climatological trace gas fields provide strong evidence that transport from the tropical upper troposphere into the layer between double tropopauses is an important pathway for stratosphere-troposphere exchange.

Kerb and urban increment of highly time-resolved trace elements in PM10, PM2.5 and PM1.0 winter aerosol in London during ClearfLo 2012

Ambient concentrations of trace elements with 2 h time resolution were measured in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 size ranges at kerbside, urban background and rural sites in London during winter 2012. Samples were collected using rotating drum impactors (RDIs) and subsequently analysed with synchrotron radiation-induced X-ray fluorescence spectrometry (SR-XRF). Quantification of kerb and urban increments (defined as kerb-to-urban and urban-to-rural concentration ratios, respectively), and assessment of diurnal and weekly variability provided insight into sources governing urban air quality and the effects of urban micro-environments on human exposure. Traffic-related elements yielded the highest kerb increments, with values in the range of 10.4 to 16.6 for SW winds (3.3–6.9 for NE) observed for elements influenced by brake wear (e.g. Cu, Sb, Ba) and 5.7 to 8.2 for SW (2.6–3.0 for NE) for other traffic-related processes (e.g. Cr, Fe, Zn). Kerb increments for these elements were highest in the PM10–2.5 mass fraction, roughly twice that of the PM1.0–0.3 fraction. These elements also showed the highest urban increments (~ 3.0), although no difference was observed between brake wear and other traffic-related elements. All elements influenced by traffic exhibited higher concentrations during morning and evening rush hours, and on weekdays compared to weekends, with the strongest trends observed at the kerbside site, and additionally enhanced by winds coming directly from the road, consistent with street canyon effects. Elements related to mineral dust (e.g. Al, Si, Ca, Sr) showed significant influences from traffic-induced resuspension, as evidenced by moderate kerb (3.4–5.4 for SW, 1.7–2.3 for NE) and urban (~ 2) increments and increased concentrations during peak traffic flow. Elements related to regional transport showed no significant enhancement at kerb or urban sites, with the exception of PM10–2.5 sea salt (factor of up to 2), which may be influenced by traffic-induced resuspension of sea and/or road salt. Heavy-duty vehicles appeared to have a larger effect than passenger vehicles on the concentrations of all elements influenced by resuspension (including sea salt) and wearing processes. Trace element concentrations in London were influenced by both local and regional sources, with coarse and intermediate fractions dominated by traffic-induced resuspension and wearing processes and fine particles influenced by regional transport.

“Pussy cat, pussy cat where have you been..?” Evaluating the use of stable isotopes, radiogenic isotopes and trace elements for investigating the ecology of Panthera leo

1. Understanding the behaviour and ecology of large carnivores is becoming increasingly important as the list of endangered species grows, with felids such as Panthera leo in some locations heading dangerously close to extinction in the wild. In order to have more reliable and effective tools to understand animal behaviour, movement and diet, we need to develop novel, integrated approaches and effective techniques to capture a detailed profile of animal foraging and movement patterns. 2. Ecological studies have shown considerable interest in using stable isotope methods, both to investigate the nature of animal feeding habits, and to map their geographical location. However, recent work has suggested that stable isotope analyses of felid fur and bone is very complex and does not correlate directly with the isotopic composition of precipitation (and hence geographical location). 3. We present new data that suggest these previous findings may be atypical, and demonstrate that isotope analyses of Felidae are suitable for both evaluating dietary inputs and establishing geo-location as they have strong environmental referents to both food and water. These data provide new evidence of an important methodology that can be applied to the family Felidae for future research in ecology, conservation, wildlife forensics and archaeological science.

Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a central European cave (NW Switzerland)

Deuterium (dD) and oxygen (d18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of 17Oexcess derived from precise measurement of d17O and d18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17Oexcess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (dD, d17O and d18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean dD, d18O and d17O are �71.0‰, �9.9‰, �5.2‰ for precipitation, �60.3‰, �8.7‰, �4.6‰ for cave drip water and �61.3‰, �8.3‰, �4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17Oexcess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (D of ~ þ 10‰ for dD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8e10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first d17O measurement in speleothem fluid inclusions, as well as the first comparison of the d17O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems. This study on precipitation, drip water and fluid inclusions will be used as a speleothem proxy calibration for Milandre cave in order to reconstruct paleotemperatures and moisture source variations for Western Central Europe.

Vehicular particulate matter emissions in road tunnels in Sao Paulo, Brazil

In the metropolitan area of Sao Paulo, Brazil, ozone and particulate matter ( PM) are the air pollutants that pose the greatest threat to air quality, since the PM and the ozone precursors ( nitrogen oxides and volatile organic compounds) are the main source of air pollution from vehicular emissions. Vehicular emissions can be measured inside road tunnels, and those measurements can provide information about emission factors of in-use vehicles. Emission factors are used to estimate vehicular emissions and are described as the amount of species emitted per vehicle distance driven or per volume of fuel consumed. This study presents emission factor data for fine particles, coarse particles, inhalable particulate matter and black carbon, as well as size distribution data for inhalable particulate matter, as measured in March and May of 2004, respectively, in the Janio Quadros and Maria Maluf road tunnels, both located in Sao Paulo. The Janio Quadros tunnel carries mainly light-duty vehicles, whereas the Maria Maluf tunnel carries light-duty and heavy-duty vehicles. In the Janio Quadros tunnel, the estimated light-duty vehicle emission factors for the trace elements copper and bromine were 261 and 220 mu g km(-1), respectively, and 16, 197, 127 and 92 mg km(-1), respectively, for black carbon, inhalable particulate matter, coarse particles and fine particles. The mean contribution of heavy-duty vehicles to the emissions of black carbon, inhalable particulate matter, coarse particles and fine particles was, respectively 29, 4, 6 and 6 times higher than that of light-duty vehicles. The inhalable particulate matter emission factor for heavy-duty vehicles was 1.2 times higher than that found during dynamometer testing. In general, the particle emissions in Sao Paulo tunnels are higher than those found in other cities of the world.

Evaluation of trace element levels in muscles, liver and gonad of fish species from Sao Francisco River of the Parana Brazilian state by using SR-TXRF technique

This study is focused on the analysis of an accumulation of inorganic elements in muscles, liver and gonad of seven fish species from Sao Francisco River located in the Parana state of Brazil. Concentrations of the elements were determined using the SR-TXRF technique. In the muscles of fish species, negative length dependent relationships were observed for chromium and zinc ion absorption. The obtained results showed that accumulated Cr ions values are above the limits defined in the Brazilian legislative norm on food. (C) 2010 Elsevier Ltd All rights reserved.

Sr-Nd isotopic evidence for crustal contamination in the Niquelandia complex, Goias, Central Brazil

The Niquelandia complex is a Neoproterozoic mafic-ultramafic intrusion resulting from fractional crystallization of primary picritic basalt intrusions. It consists of two layered sequences: a lower and larger one (LS), where four stratigraphic units exhibit an upward decrease of ultramafic layers and increase of gabbroic layers; an upper, smaller sequence (US), separated from LS by a high-temperature shear zone and consisting of two stratigraphic units (gabbros + anorthosites and amphibolites). Nd and Sr isotopic analyses and rare earth element (REE) profiles provide evidence that the complex suffered important crustal contamination. The LS isotopic array trends from a DM region with positive epsilon Nd and moderately positive epsilon Sr towards a field occupied by crustal xenoliths, especially abundant in the upper LS (negative epsilon Nd and large, positive E:Sr). Each LS stratigraphic unit is distinct from the next underlying unit, showing lower epsilon Nd and higher epsilon Sr, suggesting inputs of fresh magma and mixing with the contaminated, residual magma. The US is characterised by a relatively high variation of epsilon Nd and constant epsilon Sr. REE patterns vary within each unit from LREE depleted to LREE enriched in the samples having lower epsilon Nd and higher epsilon Sr. The contamination process has been modelled by using the EC-AFC algorithms from [Spera, F.J., Bohrson, W.A., 2001. Energy-constrained open-system magmatic processes 1: general model and energy-constrained assimilation and fractional crystallization (EC-AFC) formulation. J. Petrology 42, 999-1018]. The differences between the LS and US isotopic arrays are consistent with contamination by the same crustal component, provided that its melting degree was higher in LS than in US. The different degrees of anatexis are explained by the heat budget released from the magma, higher in LS (because of its larger mass) than in US. Comparison of the correlations between isotopes and incompatible trace element ratios of the models and of the gabbros shows some differences, which are demonstrably related with the variable amount of cumulus phases and trapped melt in the gabbros. (c) 2007 Elsevier Ltd. All rights reserved.

Major- and trace-element composition of olivine, perovskite, clinopyroxene, Cr-Fe-Ti oxides, phlogopite and host kamafugites and kimberlites, Alto Paranaiba, Brazil

An integrated whole-rock petrographic and geochemical study has been carried out on kamafugites and kimberlites of the Late Cretaceous Alto Paranaiba igneous province, in Brazil, and their main minerals, olivine, clinopyroxene, perovskite, phlogopite, spinels and ilmenite. Perovskite is by far the dominant repository for light lanthanides, Nb, Ta, Th and U, and occasionally other elements, reaching concentrations up to 3.4 x 10(4) chondrite values for light lanthanides and 105 chondrite for Th. A very strong fractionation between light and heavy lanthanides (chondrite-normalized La/Yb from similar to 175 to similar to 2000) is also observed. This is likely the first comprehensive dataset on natural perovskite. Clinopyroxene has variable trace-element contents. likely due to the different position of this phase in the crystallization sequence; Sc reaches values as high as 200 ppm whereas the lanthanides show very variable enrichment in light over heavy REE, and commonly show a negative Eu anomaly. The olivine, phlogopite (and tetra-ferriphlogopite), Cr-Ti oxide and ilmenite are substantially barren minerals for lanthanides and most other trace elements, with the exception of Ba, Cs and Rb in mica, and V, Nb and Ta in ilmenite. Estimated mineral/whole-rock partition coefficients for lanthanides in perovskite are similar to previous determinations, though much higher than those calculated in experiments with synthetic compositions, testifying once more to the complex behavior of these elements in a natural environment. The enormous potential for exploitation of lanthanides, Th, U and high-field-strength elements in the Brazilian kamafugites, kimberlites and related rocks is clearly shown.

Major- and trace-element composition of REE-rich turkestanite from peralkaline granites of the Morro Redondo Complex, Graciosa Province, south Brazil

Turkestanite, a rare Th- and REE-bearing cyclosilicate in the ekanite-steacyite group was found in evolved peralkaline granites from the Morro Redondo Complex, south Brazil. It occurs with quartz, alkali feldspar and an unnamed Y-bearing silicate. Electron microprobe analysis indicates relatively homogeneous compositions with maximum ThO(2), Na(2)O and K(2)O contents of 22.4%, 2.93% and 3.15 wt.%, respectively, and significant REE(2)O(3) abundances (5.21 to 11.04 wt.%). The REE patterns show enrichment of LREE over HREE, a strong negative Eu anomaly and positive Ce anomaly, the latter in the most transformed crystals. Laser ablation inductively coupled plasma mass spectrometry trace element patterns display considerable depletions in Nb, Zr, Hf, Ti and Li relative to whole-rock sample compositions. Observed compositional variations suggest the influence of coupled substitution mechanisms involving steacyite, a Na-dominant analogue of turkestanite, iraqite, a REE-bearing end-member in the ekanite-steacyite group, ekanite and some theoretical end-members. Turkestanite crystals were interpreted as having precipitated during post-magmatic stages in the presence of residual HFSE-rich fluids carrying Ca, the circulation of which was enhanced by deformational events.

Microgranitic Enclaves as Products of Self-mixing Events: a Study of Open-system Processes in the Maua Granite, Sao Paulo, Brazil, Based on in situ Isotopic and Trace Elements in Plagioclase

Felsic microgranular enclaves with structures indicating that they interacted in a plastic state with their chemically similar host granite are abundant in the Maua Pluton, SE Brazil. Larger plagioclase xenocrysts are in textural disequilibrium with the enclave groundmass and show complex zoning patterns with partially resorbed An-rich cores (locally with patchy textures) surrounded by more sodic rims. In situ laser ablation-(multi-collector) inductively coupled plasma mass spectrometry trace element and Sr isotopic analyses performed on the plagioclase xenocrysts indicate open-system crystallization; however, no evidence of derivation from more primitive basic melts is observed. The An-rich cores have more radiogenic initial Sr isotopic ratios that decrease towards the outermost part of the rims, which are in isotopic equilibrium with the matrix plagioclase. These profiles may have been produced by either (1) diffusional re-equilibration after rim crystallization from the enclave-forming magma, as indicated by relatively short calculated residence times, or (2) episodic contamination with a decrease of the contaminant ratio proportional to the extent to which the country rocks were isolated by the crystallization front. Profiles of trace elements with high diffusion coefficients would require unrealistically long residence times, and can be modeled in terms of fractional crystallization. A combination of trace element and Sr isotope data suggests that the felsic microgranular enclaves from the Maua Pluton are the products of interaction between end-member magmas that had similar compositions, thus recording `self-mixing` events.

U-Pb-Hf-trace element systematics and geochronology of zircon from a granulite-facies metamorphosed mafic-ultramafic layered complex in Central Brazil

Zircon recrystallization is a common process during high-grade metamorphism and promotes partial or complete resetting of the original isotopic and chemical characteristics of the mineral and thus complicates U-Pb geochronological interpretation. In Central Brazil, this complexity may be illustrated by three composite mafic-ultramafic intrusions metamorphosed under amphibolite-to-granulite conditions. Their ages of emplacement and metamorphic ages have been a matter of controversy for the last thirty years. The Serra da Malacacheta and Barro Alto complexes make up the southernmost of these layered bodies and four samples from distinct rock types were investigated in order to verify the consequences of metamorphic alteration of zircon for U-Pb dating. Cathodoluminescent imaging reveals internal features which are typical of concomitant dissolution-reprecipitation processes, such as convolute zoning and inward-moving recrystallization fronts, even in samples in which partially preserved igneous textures are observed. Due to this extensive alteration, LA-ICPMS U-Pb isotopic analysis yielded inconclusive data. However, in situ Hf isotopic and trace-element analyses help to clarify the real meaning of the geochronological data. Low Lu/Hf (<0.004) and homogeneous (176)Hf/(177)Hf(t) values imply that the zircon populations within individual samples have crystallized in a single episode, despite the observed variations in age values. Trace element signatures of zircon grains from garnet-bearing samples reveal that they were unreactive to the development of the peak metamorphism mineral assemblage and, thus, the main chemical feature in such grains is attributed to a coupled dissolution-reprecipitation process. However, in the Cafelandia amphibolite an additional alteration process is identified, probably related to the influx of late-stage fluids. Combined isotopic and geochemical investigation on zircon grains allowed the distinction of two magmatic events. The first corresponds to the crystallization of the Serra da Malacacheta Complex and characterizes a juvenile magmatism at similar to 1.3 Ga. The younger episode, recognized in the Barro Alto Complex, is dated at ca. 800 Ma and is represented by mafic and ultramafic rocks showing intense contamination with continental crust, implying that the emplacement took place, most likely, in a continental back-arc setting. Altered zircon domains as well as titanite grains date the metamorphic event at ca. 760-750 Ma. (C) 2011 Elsevier B.V. All rights reserved.

Trace element geochemistry and Sr-Nd characteristics of Mesoproterozoic mafic intrusive rocks from Rondonia, Brazil, SW Amazonian Craton: Petrogenetic and tectonic inferences

The Amazonian Craton comprises an Archean domain surrounded by four successively younger Proterozoic tectonic provinces. Within the Rio-Negro-Juruena province the Serra da Providencia Intrusive Suite (1.60 and 1.53 Ga) consists of A-type rapakivi granites, charnockites and mangerites genetically associated with diabase dikes, gabbros and amphibolites lites. The original mafic melts were derived from a depleted mantle source (epsilon(Nd(T)) + 2.5 to +2.8; epsilon(Sr(T)) - 12.1). Underplated mafic magma induced melting of a short-lived fielsic crust, thus originating coeval felsic-inafic magmatism in a continental intraplate setting. The Colorado Complex, assigned to the Rondonian-San Ignacio province, comprises 1.35-1.36 Ga intrusive bimodal magmatism represented by monzonite gneisses associated with amphibolite, gabbro and metadiabase dikes intercalated with metasediments with detrital zircon that yield U-Pb ages of 1.35 to 1.42 Ga. Mafic samples display juvenile signatures (epsilon(Nd(T)) 0.0 to +5.2; epsilon(Sr(T)) -5.0 to -30.7) and are less contaminated than the Serra da Previdencia and Nova Brasiladndia ones. The generation of the basaltic magma is related to the subduction of an oceanic slab below the peridotite wedge (intraoceanic arc setting). Fluids and/or small melts from the slab impregnated the mantle. The Nova Brasilandia Sequence (Sunsas-Aguapei province) comprises a metasedimentary sequence intruded by 1.10-1.02 Ga metadiabases, gabbros, meta-gabbros, and amphibolites associated with granitic plutons (bimodal magmatism). The original tholeiitic magmas, derived from a depleted source (epsilon(Nd(T)) = +3.1 to +5.0), in a proto-oceanic setting, underwent subsequent contamination by the host rocks, as indicated by the isotopic and trace element data.

Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the mu g m(-3) range) and their variations with sampling site and time In this work a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE) a quick separation technique that requires nothing more than some nanoliters of sample and when combined with capacitively coupled contactless conductometric detection (C(4)D) is particularly favorable for ionic species that do not absorb in the UV-vis region like the target analytes formaldehyde formic acid acetic acid and ammonium The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry s constant such as formaldehyde and carboxylic acids or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8 3 nLs(-1)) while the sample was aspirated through the annular gap of the concentric tubes at 25 mLs(-1) A second unit in all similar to the CMDS was operated as a capillary membrane diffusion emitter (CMDE) generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS The fluids of the system were driven with inexpensive aquarium air pumps and the collected samples were stored in vials cooled by a Peltier element Complete protocols were developed for the analysis in air of NH(3) CH(3)COOH HCOOH and with a derivatization setup CH(2)O by associating the CMDS collection with the determination by CE-C(4)D The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot s reaction Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW) All techniques and methods of this work are in line with the green analytical chemistry trends (C) 2010 Elsevier B V All rights reserved