Noureddine Yassaa

Evidence for marine production of monoterpenes

Environmental context. Laboratory incubation experiments and shipboard measurements in the Southern Atlantic Ocean have provided the first evidence for marine production of monoterpenes. Nine marine phytoplankton monocultures were investigated using a GC-MS equipped with an enantiomerically-selective column and found to emit monoterpenes including (–)-/(+)-pinene, limonene and p-ocimene, all of which were previously thought to be exclusively of terrestrial origin. Maximum levels of 100–200 pptv total monoterpenes were encountered when the ship crossed an active phytoplankton bloom. Abstract. Laboratory incubation experiments and shipboard measurements on the Southern Atlantic Ocean have provided the first evidence for marine production of monoterpenes. Nine marine phytoplankton monocultures were investigated using a GC-MS equipped with an enantiomerically-selective column and found to emit at rates, expressed as nmol C10H16 (monoterpene) g [chlorophyll a]–1 day–1, from 0.3 nmol g [chlorophyll a]–1 day–1 for Skeletonema costatum and Emiliania huxleyi to 225.9 nmol g [chlorophyll a]–1 day–1 for Dunaliella tertiolecta. Nine monoterpenes were identified in the sample and not in the control, namely: (–)-/(+)-pinene, myrcene, (+)-camphene, (–)-sabinene, (+)-3-carene, (–)-pinene, (–)-limonene and p-ocimene. In addition, shipboard measurements of monoterpenes in air were made in January–March 2007, over the South Atlantic Ocean. Monoterpenes were detected in marine air sufficiently far from land as to exclude influence from terrestrial sources. Maximum levels of 100–200 pptv total monoterpenes were encountered when the ship crossed an active phytoplankton bloom, whereas in low chlorophyll regions monoterpenes were mostly below detection limit.

Screening volatile organic compounds (VOCs) emissions from five marine phytoplankton species by head space gas chromatography/mass spectrometry (HS-GC/MS)

Five marine cosmopolitan phytoplankton species namely; Calcidiscus leptoporus, Emiliania huxleyi, Phaeodactylum tricornutum, Chaetoceros neogracilis and Dunaliella tertiolecta were screened for emissions of selected VOCs using head space gas chromatography/mass spectrometry (HS-GC/MS) in single ion mode. The VOCs investigated included isoprene and various halogenated compounds. Among the different algae groups, the two diatoms Ch. neogracilis and P. tricornutum were the strongest emitters of methyl bromide (CH3Br), and Ch. neogracilis was the strongest emitter of isoprene. Furthermore, we present evidence that several chlorinated organic compounds, normally considered as anthropogenic, can be produced from marine phytoplankton (namely chloroform, dichloromethane, trichloroethylene, tetrachloroethylene, chlorobenzene and dichlorobenzene).

Atmospheric benzenoid emissions from plants rival those from fossil fuels

Despite the known biochemical production of a range of aromatic compounds by plants and the presence of benzenoids in floral scents, the emissions of only a few benzenoid compounds have been reported from the biosphere to the atmosphere. Here, using evidence from measurements at aircraft, ecosystem, tree, branch and leaf scales, with complementary isotopic labeling experiments, we show that vegetation (leaves, flowers, and phytoplankton) emits a wide variety of benzenoid compounds to the atmosphere at substantial rates. Controlled environment experiments show that plants are able to alter their metabolism to produce and release many benzenoids under stress conditions. The functions of these compounds remain unclear but may be related to chemical communication and protection against stress. We estimate the total global secondary organic aerosol potential from biogenic benzenoids to be similar to that from anthropogenic benzenoids (~10 Tg y−1), pointing to the importance of these natural emissions in atmospheric physics and chemistry.

Isoprene emission from phytoplankton monocultures: the relationship with chlorophyll-a, cell volume and carbon content

We report here isoprene emission rates determined from various phytoplankton cultures incubated under PAR light which was varied so as to simulate a natural diel cycle. Phytoplankton species representative of different phytoplankton functional types (PFTs) namely: cyanobacteria, diatoms, coccolithophorides, and chlorophytes have been studied. Biomass normalised isoprene emission rates presented here relative to the chlorophyll-a (Chl-a) content of the cultures showed that the two cyanobacteria (Synechococcus and Trichodesmium) were the strongest emitters with emission rates in the range of 17 to 28 mu g C(5)H(8) g(-1) Chl-a h(-1). Diatoms produced isoprene in a significantly lower emission range: 3 to 7.5 mu g C(5)H(8) g(-1) Chl-a h(-1) and Dunaliella tertiolecta was by far the lowest emitter of our investigated plankton cultures. Despite the group specific differences observed, a high emission rate variance was observed to occur within one phytoplankton group. However, a combination of literature and our own data showed a clear relationship between the actual cell volume and the isoprene emission rates. This relationship could be a valuable tool for future modelling approaches of global isoprene emissions.

Evaluation of monoterpenic biogenic volatile organic compounds in ambient air around Eucalyptus globulus, Pinus halepensis and Cedrus atlantica trees growing in Algiers city area by chiral and achiral capillary gas chromatography

Abstract The monoterpenic biogenic volatile organic compounds (BVOCs) in ambient air around either Eucalyptus globulus, Cedrus atlantica and Pinus halepensis trees from El- Hamma Botanical Garden (Algiers) or from Pinus halepensis trees field located in Bab-Ezzouar (suburb of Algiers) was qualitatively and semi-quantitatively evaluated. The sampling was carried out in ambient air by adsorption through an activated charcoal cartridge followed by the carbon disulfide extraction. The solution was subjected to high-resolution gas chromatography (HRGC) analysis in programmed temperature. The identification of the components was established by the means of retention Kovats indexes. The use of a β-cyclodextrin chiral capillary column allowed a good separation of monoterpenic enantiomers released in the atmosphere. The enantiomeric ratio provided a good insight into the enantiomeric compound preferentially emitted by plants.

Assessing the effect of marine isoprene and ship emissions on ozone, using modelling and measurements from the South Atlantic Ocean

Environmental context. Air over the remote Southern Atlantic Ocean is amongst the cleanest anywhere on the planet. Yet in summer a large-scale natural phytoplankton bloom emits numerous natural reactive compounds into the overlying air. The productive waters also support a large squid fishing fleet, which emits significant amounts of NO and NO2. The combination of these natural and man-made emissions can efficiently produce ozone, an important atmospheric oxidant. Abstract. Ship-borne measurements have been made in air over the remote South Atlantic and Southern Oceans in January–March 2007. This cruise encountered a large-scale natural phytoplankton bloom emitting reactive hydrocarbons (e.g. isoprene); and a high seas squid fishing fleet emitting NOx (NO and NO2). Using an atmospheric chemistry box model constrained by in-situ measurements, it is shown that enhanced ozone production ensues from such juxtaposed marine biogenic and anthropogenic emissions. The relative impact of shipping and phytoplankton emissions on ozone was examined on a global scale using the EMAC model. Ozone in the marine boundary layer was found to be over ten times more sensitive to NOx emissions from ships, than to marine isoprene in the region south of 45°. Although marine isoprene emissions make little impact on the global ozone budget, co-located ship and phytoplankton emissions may explain the increasing ozone reported for the 40–60°S southern Atlantic region.

Possible evidence for a connection between methyl iodide emissions and Saharan dust

Methyl iodide has been measured during two field campaigns in the Atlantic region in 2002. The first took place in July–August at 2300 m on the island of Tenerife, while the second was a shipborne, east–west crossing of the Tropical Atlantic at 10°N in October–November of the same year. Both campaigns were periodically impacted by dust, advected from Africa in trade winds. Unexpectedly, during these dust events, methyl iodide mixing ratios were observed to be high relative to other times. Backward calculations with the particle dispersion model FLEXPART show the origin of the dust storms as Mauritania and southern Algeria for the ground- and ship-based campaigns, respectively. The dust-laden air traveled from its source above the marine boundary layer to the measurement region. On the basis of the field data correlations and the simulations, we suggest that dust-stimulated emission of methyl iodide has occurred. To test this hypothesis, dust samples were collected from the identified source regions and added to filtered Atlantic seawater. This rapidly produced methyl iodide. Further tests established that the addition of iodide increased the yield and that iodide with H2O2 was greater still. This was found for both sterilized and nonsterilized samples. We conclude that there is an abiotic methyl iodide production mechanism that can occur via substitution, analogous to those in soil, rather than radical recombination. This may occur when dust contacts seawater containing iodide or when marine water vapor condenses on dust containing iodide. This hypothesis appears to be consistent with recent long-term methyl iodide data sets from Tasmania and may help resolve current uncertainties in the iodine cycle.

Organic components of Algerian desert dusts.

The organic fraction associated to sands of five localities of Algerian Sahara Desert was characterized with regards to n-alkanes, polynuclear aromatic hydrocarbons (PAH) and mono/dicarboxylic acids. Huge differences were observed among total contents of the three groups in the sands and, within each group, with regard to percent distribution patterns of congeners. Mutagenic nitro-PAH were virtually absent. Organic acids were identified as the most abundant compounds in all samples (up to 4800 ng g(-1) vs. less than 700 of n-alkanes and 22 ng g(-1) of PAH); their presence was overall related to biogenic sources except for the Hassi Messaoud petroleum area, where an important contribution of anthropogenic emission was present. The sand composition at Hassi Messaoud (and, at lesser extent, Tougguort) seemed to indicate that environmental conditions promote there the oxidative decomposition of organics; by contrast, at Laghouat, Hassi Bahbah and Gardaïa oases the deposition involved fresh (non-reacted) air pollutants. The sand composition at the Hassi Messaoud was compared to that of airborne particulates of the industrial district and city. Airborne n-alkanes (≈500 ng m(-3)) and fatty acids (≈15000 ng m(-3)) were very high compared to Algiers city, whilst PAH contents (10-60 ng m(-3)) were typical of polluted areas in winter; similarly, the sands were reach of the two aliphatic groups and relatively poor of PAH.

Fast determination of methyl chloride and methyl bromide emissions from dried plant matter and soil samples using HS-SPME and GC-MS: method and first results

Environmental context. Headspace solid-phase microextraction (HS-SPME) and analysis by gas chromatography–mass spectrometry (GC/MS) system has been employed for quantifying the emissions of methyl chloride (CH3Cl) and methyl bromide (CH3Br) from plants and soils. Compared with more commonly used techniques, HS-SPME coupled to GC/MS is simple, fast, sensitive, economical and non-destructive, with potential for laboratory-based and field studies. Abstract. Headspace solid-phase microextraction (HS-SPME) and gas chromatography–mass spectrometry (GC/MS) system have been employed for quantifying the emissions of methyl chloride (CH3Cl) and methyl bromide (CH3Br) from plants and soils. Seven SPME fibre coatings including 75 μm Carboxen-polydimethylsiloxane (CAR-PDMS), 85 μm Carboxen-PDMS (CAR-PDMS), 50/30 μm divinylbenzene-CAR-PDMS (DVB-CAR-PDMS), 65 μm DVB-PDMS, 65 μm carbowax-DVB (CW-DVB), 30 μm PDMS (PDMS) and 100 μm PDMS, were tested by comparing their sampling efficiencies towards CH3Cl and CH3Br. Key parameters such as extraction time, desorption temperature and time were all optimised in this work. The optimum conditions were found with CAR-PDMS 75 μm as an SPME fibre coating, a 1-min sampling time, a 50°C incubation temperature and a 2-min desorption time and a 250°C desorption temperature. These conditions were used for the determination of CH3Cl and CH3Br emission rates from different plant species as well as soil samples. Compared with more commonly used techniques, HS-SPME coupled to GC/MS is simple, fast, sensitive, economical and non-destructive, with potential for laboratory-based and field studies.

Analysis of volatile organic compounds in the ambient air of Algiers by gas chromatography with a β-cyclodextrin capillary column

The concentrations of para- and meta-xylenes were given together in the majority of measurements of volatile organic compounds (VOCs) because of nonseparation of these two compounds by gas chromatography in usual capillary columns. In order to improve the separation of VOCs in ambient air, a β-cyclodextrin capillary column was used. The pollutants were sampled by two methods, i.e., adsorption on a charcoal cartridge followed by liquid extraction and solid-phase microextraction. About 26 VOCs, mainly aromatics, were identified in urban air of Algiers. The use of a β-cyclodextrin column allowed good separation of aromatic hydrocarbons, as well as of para- and meta-xylenes. Inversion of elution order was also observed regarding the other aromatics, in particular ethylbenzene and meta- and para-xylenes.