Assessment of trace metal air pollution in Paris using slurry-TXRF analysis on cemetery mosses

Mosses are useful, ubiquitous accumulation biomonitors and as such can be used for biomonitoring surveys. However, the biomonitoring of atmospheric pollution can be compromised in urban contexts if the targeted biomonitors are regularly disturbed, irregularly distributed, or are difficult to access. Here, we test the hypothesis that cemeteries are appropriate moss sampling sites for the evaluation of air pollution in urban areas. We sampled mosses growing on gravestones in 21 urban and peri-urban cemeteries in the Paris metropolitan area. We focused on Grimmia pulvinata (Hedwig) Smith, a species abundantly found in all studied cemeteries and very common in Europe. The concentration of Al, As, Br, Ca, Ce, Cl, Cr, Cu, Fe, K, Mn, Ni, V, P, Pb, Rb, S, Sr, Ti, and Zn was determined by a total reflection X-ray fluorescence technique coupled with a slurry sampling method (slurry-TXRF). This method avoids a digestion step, reduces the risk of sample contamination, and works even at low sample quantities. Elemental markers of road traffic indicated that the highest polluted cemeteries were located near the highly frequented Parisian ring road and under the influence of prevailing winds. The sites with the lowest pollution were found not only in the peri-urban cemeteries, adjoining forest or farming landscapes, but also in the large and relatively wooded cemeteries located in the center of Paris. Our results suggest that (1) slurry-TXRF might be successfully used with moss material, (2) G. pulvinata might be a good biomonitor of trace metals air pollution in urban context, and (3) cemetery moss sampling could be a useful complement for monitoring urban areas.

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Graphical abstract We tested the hypothesis that cemeteries are appropriate moss sampling sites for the evaluation of air pollution in urban areas. We sampled 110 moss cushions (Grimmia pulvinata) growing on gravestones in 21 urban and peri-urban cemeteries in the Paris metropolitan area. The concentration of 20 elements in mosses was determined by a total reflection X-ray fluorescence technique coupled with a slurry sampling method. Statistical analysis revealed that: - Urbanized Parisian areas crossed by traffic roads have the highest polluted cemeteries with a strong influence of main wind direction on the distribution of air pollutants - As expected, small cemeteries with low tree density were heavily polluted - Less obvious, large green spaces such as large cemeteries (Père Lachaise, Montmartre, Montparnasse) in the center of a dense metropolis like Paris present the same level of atmospheric trace metal pollution as cemeteries in less urbanized areas or nearing a very large forest. This suggests that even in densely urbanized areas, there is more spatial variability in pollution distribution than usually assumed and that large urban areas with low traffic and green filters such as trees are likely to intercept air pollutants

     

A framework for understanding climate change impacts on coral reef social–ecological systems

Corals and coral-associated species are highly vulnerable to the emerging effects of global climate change. The widespread degradation of coral reefs, which will be accelerated by climate change, jeopardizes the goods and services that tropical nations derive from reef ecosystems. However, climate change impacts to reef social–ecological systems can also be bi-directional. For example, some climate impacts, such as storms and sea level rise, can directly impact societies, with repercussions for how they interact with the environment. This study identifies the multiple impact pathways within coral reef social–ecological systems arising from four key climatic drivers: increased sea surface temperature, severe tropical storms, sea level rise and ocean acidification. We develop a novel framework for investigating climate change impacts in social–ecological systems, which helps to highlight the diverse impacts that must be considered in order to develop a more complete understanding of the impacts of climate change, as well as developing appropriate management actions to mitigate climate change impacts on coral reef and people.     

The food-print of Paris: long-term reconstruction of the nitrogen flows imported into the city from its rural hinterland

Between the tenth and twentieth century the population of Paris city increased from a few thousand to near 10 million inhabitants. In response to the growing urban demand during this period, the agrarian systems of the surrounding rural areas tremendously increased their potential for commercial export of agricultural products, made possible by a surplus of agricultural production over local consumption by humans and livestock in these areas. Expressed in terms of nitrogen, the potential for export increased from about 60 kg N/km2/year of rural territory in the Middle Ages, to more than 5,000 kg N/km2/year from modern agriculture. As a result of the balance between urban population growth and rural productivity, the rural area required to supply Paris (i.e. its food-print) did not change substantially for several centuries, remaining at the size of the Seine watershed surrounding the city (around 60,000 km2). The theoretical estimate of the size of the supplying hinterland at the end of the eighteenth century is confirmed by the figures deduced from the analysis of the historical city toll data (octroi). During the second half of the twentieth century, the ‘food-print’ of Paris reduced in size, owing to an unprecedented increase in the potential for commercial export associated with modern agricultural systems based on chemical N fertilization. We argue that analysing the capacity of territories to satisfy the demand for nitrogen-containing food products of local or distant urban population and markets might provide new and useful insights when assessing world food resource allocation in the context of increasing population and urbanization.     

Hg concentrations and related risk assessment in coral reef crustaceans, molluscs and fish from New Caledonia

There is a dramatic lack of data on Hg levels in marine organisms from tropical areas, and in particular from New Caledonia. For the first time, this study reports the total Hg concentrations in the tissues of several marine taxa from the New Caledonian lagoon. Seafood from both wild and farmed populations was considered. Hg concentrations varied over three orders of magnitudes according to factors including species, age (size/weight), trophic level, lifestyle and geographical origin. Taking into account the edible tissues, estimations of the amount of flesh that should be consumed by a 60-kg person to reach the Hg Provisional Tolerable Weekly Intake (PTWI) reveal acceptable risk for Human health in general. However, a risk was clearly identified in one site of the lagoon (i.e. Grande Rade) where high Hg concentrations were measured. These concentrations were higher than values reported in the current literature.     

Isolation and characterization of mesotrione-degrading Bacillus sp. from soil

Dissipation kinetics of mesotrione, a new triketone herbicide, sprayed on soil from Limagne (Puy-de-Dôme, France) showed that the soil microflora were able to biotransform it.Bacteria from this soil were cultured in mineral salt solution supplemented with mesotrione as sole source of carbon for the isolation of mesotrione-degrading bacteria. The bacterial community structure of the enrichment cultures was analyzed by temporal temperature gradient gel electrophoresis (TTGE). The TTGE fingerprints revealed that mesotrione had an impact on bacterial community structure only at its highest concentrations and showed mesotrione-sensitive and mesotrione-adapted strains. Two adapted strains, identified as Bacillus sp. and Arthrobacter sp., were isolated by colony hybridization methods.Biodegradation assays showed that only the Bacillus sp. strain was able to completely and rapidly biotransform mesotrione. Among several metabolites formed, 2-amino-4-methylsulfonylbenzoic acid (AMBA) accumulated in the medium. Although sulcotrione has a chemical structure closely resembling that of mesotrione, the isolates were unable to degrade it.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

Wood smoke as a source of particle-phase organic compounds in residential areas

The objective of this study was to investigate the organic composition of wood smoke emissions and ambient air samples in order to determine the wood smoke contribution to the ambient air pollution in the residential areas. From November 2005 to March 2006 particle-phase PM₁₀ samples were collected in the residential town Dettenhausen surrounded by forests near Stuttgart in southern Germany. Samples collected on pre-baked glass fibre filters were extracted using toluene with ultrasonic bath and analysed by gas chromatography mass spectrometry (GC-MS). 21 polycyclic aromatic hydrocarbons (PAH) including 16 USEPA priority pollutants, different organic wood smoke tracers, primarily 21 species of syringol and guaiacol derivatives, levoglucosan and its isomers mannosan, galactosan and dehydroabietic acid were detected and quantified in this study. The concentrations of these compounds were compared with the fingerprints of emissions from hardwood and softwood combustion carried out in test facilities at Universitaet Stuttgart and field investigations at a wood stove during real operation in Dettenhausen. It was observed that the combustion derived PAH was detected in higher concentrations than other PAH in the ambient air PM₁₀ samples. Syringol and its derivatives were found in large amounts in hardwood burning but were not detected in softwood burning emissions. On the other hand, guaiacol and its derivatives were found in both softwood and hardwood burning emissions, but the concentrations were higher in the softwood smoke compared to hardwood smoke. So, these compounds can be used as typical tracer compounds for the different types of wood burning emissions. In ambient air samples both syringol and guaiacol derivatives were found which indicates the wood combustion contribution to the PM load in such residential areas. Levoglucosan was detected in high concentrations in all ambient PM₁₀ samples. A source apportionment modelling, Positive Matrix Factorization (PMF) was implemented to quantify the wood smoke contribution to the ambient PM₁₀ bound organic compounds in the residential area.     

Gas-phase chemistry of benzyl alcohol: Reaction rate constants and products with OH radical and ozone

A bimolecular rate constant, k_{OH+Benzyl alcohol}, of (28 ± 7) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with benzyl alcohol, at (297 ± 3) K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k_{O3+Benzyl alcohol}, of approximately 6 × 10^?19 cm³ molecule^?1 s^?1 was determined by monitoring the decrease in benzyl alcohol concentration over time in an excess of ozone (O₃). To more clearly define part of benzyl alcohol's indoor environment degradation mechanism, the products of the benzyl alcohol + OH were also investigated. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to positively identify benzaldehyde, glyoxal and 4-oxopentanal as benzyl alcohol/OH reaction products. The elucidation of other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible benzyl alcohol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.     

Aerosol formation yields from the reaction of catechol with ozone

The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (M_o) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm^?3. Analysis of the data clearly shows that Y is a strong function of M_o and that secondary organic aerosol formation can be expressed by a one-product gas–particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.