Chemical interaction of atmospheric mineral dust-derived nanoparticles with natural seawater — EPS and sunlight-mediated changes

Laboratory studies were conducted to investigate the interactions of nanoparticles (NPs) formed via simulated cloud processing of mineral dust with seawater under environmentally relevant conditions. The effect of sunlight and the presence of exopolymeric substances (EPS) were assessed on the: (1) colloidal stability of the nanoparticle aggregates (i.e. size distribution, zeta potential, polydispersity); (2) micromorphology and (3) Fe dissolution from particles. We have demonstrated that: (i) synthetic nano-ferrihydrite has distinct aggregation behaviour from NPs formed from mineral dusts in that the average hydrodynamic diameter remained unaltered upon dispersion in seawater (~1500 nm), whilst all dust derived NPs increased about three fold in aggregate size; (ii) relatively stable and monodisperse aggregates of NPs formed during simulated cloud processing of mineral dust become more polydisperse and unstable in contact with seawater; (iii) EPS forms stable aggregates with both the ferrihydrite and the dust derived NPs whose hydrodynamic diameter remains unchanged in seawater over 24h; (iv) dissolved Fe concentration from NPs, measured here as <3 kDa filter-fraction, is consistently >30% higher in seawater in the presence of EPS and the effect is even more pronounced in the absence of light; (v) micromorphology of nanoparticles from mineral dusts closely resemble that of synthetic ferrihydrite in MQ water, but in seawater with EPS they form less compact aggregates, highly variable in size, possibly due to EPS-mediated steric and electrostatic interactions. The larger scale implications on real systems of the EPS solubilising effect on Fe and other metals with the additional enhancement of colloidal stability of the resulting aggregates are discussed.

An estimate of the global emissions of methyl bromide from automobile exhausts

An estimate of the annual global methyl bromide (CH3Br) emissions from automobile exhausts has been determined by extrapolating the results of a field study conducted in the United Kingdom (UK). A strong linear correlation was observed between the CH3Br and carbon monoxide (CO) concentrations of roadside air in three cities. This correlation and knowledge of the UK CO emissions was used to estimate the source strength of CH3Br from automobile exhausts in the UK (0.04 ktonnes yr−1). Further extrapolations lead to a value of 1.5 ktonnes yr−1 (with an upper limit of 3.0 ktonnes yr−1) of CH3Br released globally to the atmosphere from automobile exhausts.

Recovery from TBT pollution in English Channel environments: A problem solved?

Following recognition of effects in the 1980s, tributyltin (TBT) has been monitored at sites in the English Channel to evaluate the prognosis for biota – spanning the introduction of restrictions on TBT use on small boats and the recent phase-out on the global fleet. We describe how persistence and impact of TBT in clams Scrobicularia plana has changed during this period in Southampton Water and Poole Harbour. TBT contamination (and loss) in water, sediment and clams reflects the abundance and type of vessel activity: half-times in sediment (up to 8y in Poole, 33y in Southampton) are longest near commercial shipping. Recovery of clam populations – slowest in TBT-contaminated deposits – provides a useful biological measure of legislative efficacy in estuaries. On rocky shores, recovery from imposex in Nucella lapillus is evident at many sites but, near ports, is prolonged by shipping impacts, including sediment legacy, for example, in the Fal.

Global oceanic emission of ammonia: Constraints from seawater and atmospheric observations

Current global inventories of ammonia emissions identify the ocean as the largest natural source. This source depends on seawater pH, temperature, and the concentration of total seawater ammonia (NHx(sw)), which reflects a balance between remineralization of organic matter, uptake by plankton, and nitrification. Here we compare [NHx(sw)] from two global ocean biogeochemical models (BEC and COBALT) against extensive ocean observations. Simulated [NHx(sw)] are generally biased high. Improved simulation can be achieved in COBALT by increasing the plankton affinity for NHx within observed ranges. The resulting global ocean emissions is 2.5 TgN a−1, much lower than current literature values (7–23 TgN a−1), including the widely used Global Emissions InitiAtive (GEIA) inventory (8 TgN a−1). Such a weak ocean source implies that continental sources contribute more than half of atmospheric NHx over most of the ocean in the Northern Hemisphere. Ammonia emitted from oceanic sources is insufficient to neutralize sulfate aerosol acidity, consistent with observations. There is evidence over the Equatorial Pacific for a missing source of atmospheric ammonia that could be due to photolysis of marine organic nitrogen at the ocean surface or in the atmosphere. Accommodating this possible missing source yields a global ocean emission of ammonia in the range 2–5 TgN a−1, comparable in magnitude to other natural sources from open fires and soils.

Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry of the ultraviolet screening pigment scytonemin: characteristic fragmentations

Atmospheric pressure chemical ionisation reversed-phase high-performance liquid chromatography/multistage mass spectrometry has been used to study the mass spectral fragmentation of the cyanobacterial sheath pigment scytonemin and its reduced counterpart. The two pigments exhibit characteristic fragment ions in their MS2 and MS3 spectra that are of value in confirming the identification of the structures in extracts from natural environments.

Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry of bacteriochlorophylls from Chlorobiaceae: characteristic fragmentations

Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry/mass spectrometry (APCI-LC/MS/MS) has been applied to the study of bacteriochlorophylls c, d, and e of phototrophic prokaryotes. Cultures of Chlorobiaceae containing bacteriochlorophyll c, d or e were examined using a high-resolution high-performance liquid chromatography (HPLC) method and APCI-LC/MS/MS employing post-column addition of formic acid. The results reveal complex distributions of bacteriochlorophyll homologues, with some closely eluting species giving isobaric protonated molecules. On-line LC/MS/MS studies reveal characteristic fragment ions for bacteriochlorophylls c, d, and e. Fragmentations involving loss of the extended alkyl substituents that are unique to bacteriochlorophylls c, d and e and their derivatives have been rationalised by studying the phaeophorbides and the results applied to the direct study of the bacteriochlorophylls.

Vertical fluxes and atmospheric cycling of methanol, acetaldehyde, and acetone in a coastal environment

We present here vertical fluxes of methanol, acetaldehyde, and acetone measured directly with eddy covariance (EC) during March to July 2012 near the southwest coast of the UK. The performance of the proton-transfer reaction mass spectrometer (PTR-MS) for flux measurement is characterized, with additional considerations given to the homogeneity and stationarity assumptions required by EC. Concentrations and fluxes of these compounds vary significantly with time of day and wind direction. Higher values of acetaldehyde and acetone are usually observed in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol concentration and flux do not demonstrate clear diel variability, suggesting sources in addition to plants. We estimate air–sea exchange and photochemical rates of these compounds, which are compared to measured vertical fluxes. For acetaldehyde, the mean (1�) concentration of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction outpaces production during the day. Air-sea exchange and photochemistry are probably net sinks of methanol and acetone in this region. Their nighttime concentrations of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long distance transport, respectively.

Attribution of Atmospheric Sulfur Dioxide over the English Channel to Dimethylsulfide and Changing Ship Emissions

Atmospheric sulfur dioxide (SO2) was measured continuously from the Penlee Point Atmospheric Observatory(PPAO) near Plymouth, United Kingdom between May 2014 and November 2015. This coastal site is exposed to marine air across a wide wind sector. The predominant southwesterly winds carry relatively clean background Atlantic air. In contrast, air from the southeast is heavily influenced by exhaust plumes from ships in the English Channel as well as near the Plymouth Sound. New International Maritime Organization (IMO) regulation came into force in January 2015 to reduce sulfur emissions tenfold in Sulfur Emission Control Areas such as the English Channel. Our observations suggest a three-fold reduction from 2014 to 2015 in ship-emitted SO2 from that direction. Apparent fuel sulfur content calculated from coincidental SO2 and carbon dioxide (CO2) peaks from local ship plum es show a high level of compliance to the IMO regulation (> 95 %) in both years. Dimethylsulfide (DMS) is an important source of atmospheric SO2 even in this semi-polluted region. The relative contribution of DMS oxidation to the SO2 burden over the English Channel increased from ~ 1/3 in 2014 to ~ 1/2 in 2015 due to the reduction in ship sulfur emissions. Our diel analysis suggests that SO2 is removed from the marine atmospheric boundary layer in about half a day, with dry deposition to the ocean accounting for a quarter of the total loss.

Estimation of chlorophyll degradation into phaeophytinin Anaptychia ciliaris as a method to detect air pollution

Se estudia la influencia de los siguientes factores sobre el valor del cociente de feofitinización DO 435 nm/DO 415 nm en el líquen Anaptychia ciliaris (L.) Kórber: edad del líquen, concentración final de pigmentos, trasplante de los líquenes a áreas distintas sobre sustratos diferentes o similares y el valor de pH del sustrato original o el adoptado tras el trasplante. Se discute la utilización de A. ciliaris como un bioindicador de la presencia de factorcs acidificantes en la atmósfera o en el agua de lluvia que provoquen la feofitinización de las clorofilas.

Biomonitoring of air pollutants by using lichens (Evernia prunastri) in areas between Kenitra and Mohammedia cities in Morocco.

In this study, Evernia prunastri, a lichen growing in its natural habitat in Morocco was analysed for the concentration of five heavy metals (Fe, Pb, Zn, Cu and Cr) from eleven sites between Kenitra and Mohammedia cities. The control site was Dar Essalam, an isolated area with low traffic density and dense vegetation. In the investigated areas, the concentration of heavy metals was correlated with vehicular traffic, industrial activity and urbanization. The total metal concentration was highest in Sidi Yahya, followed by Mohammedia and Bouznika. The coefficient of variation was higher for Pb and lower for Cu, Zn and Fe. The concentrations of most heavy metals in the thalli differed significantly between sites (p<0.01). Principal component analysis (PCA) revealed a significant correlation between heavy metal accumulation and atmospheric purity index. This study demonstrated also that the factors most strongly affecting the lichen flora were traffic density, the petroleum industry and paper factories in these areas. Overall, these results suggest that the index of atmospheric purity and assessment of heavy metals in lichen thalli are good indicators of the air quality at the studied sites.