Carme Bosch

Sources of black carbon to the Himalayan–Tibetan Plateau glaciers

Combustion-derived black carbon (BC) aerosols accelerate glacier melting in the Himalayas and in Tibet (the Third Pole (TP)), thereby limiting the sustainable freshwater supplies for billions of people. However, the sources of BC reaching the TP remain uncertain, hindering both process understanding and efficient mitigation. Here we present the source-diagnostic Δ14C/δ13C compositions of BC isolated from aerosol and snowpit samples in the TP. For the Himalayas, we found equal contributions from fossil fuel (46±11%) and biomass (54±11%) combustion, consistent with BC source fingerprints from the Indo-Gangetic Plain, whereas BC in the remote northern TP predominantly derives from fossil fuel combustion (66±16%), consistent with Chinese sources. The fossil fuel contributions to BC in the snowpits of the inner TP are lower (30±10%), implying contributions from internal Tibetan sources (for example, yak dung combustion). Constraints on BC sources facilitate improved modelling of climatic patterns, hydrological effects and provide guidance for effective mitigation actions.

Source-diagnostic dual-isotope composition and optical properties of water-soluble organic carbon and elemental carbon in the South Asian outflow intercepted over the Indian Ocean

The dual carbon isotope signatures and optical properties of carbonaceous aerosols have been investigated simultaneously for the first time in the South Asian outflow during an intensive campaign at the Maldives Climate Observatory on Hanimaadhoo (MCOH) (February and March 2012). As one component of the Cloud Aerosol Radiative Forcing Dynamics Experiment, this paper reports on the sources and the atmospheric processing of elemental carbon (EC) and water-soluble organic carbon (WSOC) as examined by a dual carbon isotope approach. The radiocarbon (C-14) data show that WSOC has a significantly higher biomass/biogenic contribution (865%) compared to EC (594%). The more C-13-enriched signature of MCOH-WSOC (-20.80.7) compared to MCOH-EC (-25.8 +/- 0.3 parts per thousand) and megacity Delhi WSOC (-24.1 +/- 0.9 parts per thousand) suggests that WSOC is significantly more affected by aging during long-range transport than EC. The C-13-C-14 signal suggests that the wintertime WSOC intercepted over the Indian Ocean largely represents aged primary biomass burning aerosols. Since light-absorbing organic carbon aerosols (Brown Carbon (BrC)) have recently been identified as potential contributors to positive radiative forcing, optical properties of WSOC were also investigated. The mass absorption cross section of WSOC (MAC(365)) was 0.5 +/- 0.2 m(2)g(-1) which is lower than what has been observed at near-source sites, indicating a net decrease of WSOC light-absorption character during long-range transport. Near-surface WSOC at MCOH accounted for similar to 1% of the total direct solar absorbance relative to EC, which is lower than the BrC absorption inferred from solar spectral observations of ambient aerosols, suggesting that a significant portion of BrC might be included in the water-insoluble portion of organic aerosols.

Identification of water soluble and particle bound compounds causing sublethal toxic effects. A field study on sediments affected by a chlor-alkali industry

A combination of cost effective sublethal Daphnia magna feeding tests, yeast- and cell culture-based bioassays and Toxicity Identification Evaluation (TIE) procedures was used to characterize toxic compounds within sediments collected in a river area under the influence of the effluents from a chlor-alkali industry (Ebro River, NE Spain). Tests were designed to measure and identify toxic compounds in the particulate and filtered water fractions of sediment elutriates. The combined use of bioassays responding to elutriates and dioxin-like compounds evidenced the existence of three major groups of hazardous contaminants in the most contaminated site: (A) metals such as cadmium and mercury bound to sediment fine particles that could be easily resuspended and moved downstream, (B) soluble compounds (presumably, lye) able to alkalinize water to toxic levels, and (C) organochlorine compounds with high dioxin-like activity. These results provided evidence that elutriate D. magna feeding responses can be used as surrogate assays for more tedious chronic whole sediment tests, and that the incorporation of such tests in sediment TIE procedures may improve the ability to identify the toxicity of particle-bound and water-soluble contaminants in sediments.

Radiocarbon-based source apportionment of elemental carbon aerosols at two South Asian receptor observatories over a full annual cycle

Black carbon (BC) aerosols impact climate and air quality. Since BC from fossil versus biomass combustion have different optical properties and different abilities to penetrate the lungs, it is important to better understand their relative contributions in strongly affected regions such as South Asia. This study reports the first year-round 14C-based source apportionment of elemental carbon (EC), the mass-based correspondent to BC, using as regional receptor sites the international Maldives Climate Observatory in Hanimaadhoo (MCOH) and the mountaintop observatory of the Indian Institute of Tropical Meteorology in Sinhagad, India (SINH). For the highly-polluted winter season (December–March), the fractional contribution to EC from biomass burning (fbio) was 53 ± 5% (n = 6) at MCOH and 56 ± 3% at SINH (n = 5). The fbio for the non-winter remainder was 53 ± 11% (n = 6) at MCOH and 48 ± 8% (n = 7) at SINH. This observation-based constraint on near-equal contributions from biomass burning and fossil fuel combustion at both sites compare with predictions from eight technology-based emission inventory (EI) models for India of (fbio)EI spanning 55–88%, suggesting that most current EI for Indian BC systematically under predict the relative contribution of fossil fuel combustion. A continued iterative testing of bottom-up EI with top-down observational source constraints has the potential to lead to reduced uncertainties regarding EC sources and emissions to the benefit of both models of climate and air quality as well as guide efficient policies to mitigate emissions.

Integrated biological and chemical analysis of organochlorine compound pollution and of its biological effects in a riverine system downstream the discharge point.

Pollution in riverine systems, along with its biological effects, may propagate downstream even at considerable distances. We analyzed the organochlorine compound (OC) pollution in a section of the low Ebro River (Northeast Spain) downstream a long-operating chlor-alkali plant. Maximal levels of OCs and of their associated dioxin-like biological activity occurred in residue samples from the plant, and persisted in river sediments some 40km downstream (Xerta site). Biological analysis at multiple organization levels in local carp (Cyprinus carpio, EROD, Cyp1A mRNA expression in the liver, hepatosomatic index, condition factor, and micronuclei index in peripheral blood) showed a similar pattern, with a maximal impact in Ascó, few kilometers downstream the plant, and a clear reduction at Xerta. This combination of chemical, molecular, cellular and physiological data allowed the precise assessment of the negative impact of the chlor-alkali plant on the quality of river sediments and on fish, and suggests that sediments may be a reservoir for toxic substances even in dynamic environments like rivers.

Source Apportionment of Polycyclic Aromatic Hydrocarbons in Central European Soils with Compound-Specific Triple Isotopes (δ13C, Δ14C, and δ2H)

This paper reports the first study applying a triple-isotope approach for source apportionment of polycyclic aromatic hydrocarbons (PAHs). The (13)C/(12)C, (14)C/(12)C, and (2)H/(1)H isotope ratios of PAHs were determined in forest soils from mountainous areas of the Czech Republic, European Union. Statistical modeling applying a Bayesian Markov chain Monte Carlo (MCMC) framework to the environmental triple isotope PAH data and an end-member PAH isotope database allowed comprehensive accounting of uncertainties and quantitative constraints on the PAH sources among biomass combustion, liquid fossil fuel combustion, and coal combustion at low and high temperatures. The results suggest that PAHs in this central European region had a clear predominance of coal combustion sources (75 ± 6%; uncertainties represent 1 SD), mainly coal pyrolysis at low temperature (∼650 °C; 61 ± 8%). Combustion of liquid fossil fuels and biomass represented 16 ± 3 and 9 ± 3% of the total PAH burden (∑PAH14), respectively. Although some soils were located close to potential PAH point sources, the source distribution was within a narrow range throughout the region. These observation-based top-down constraints on sources of environmental PAHs provide a reference for both improved bottom-up emission inventories and guidance for efforts to mitigate PAH emissions.

Important fossil source contribution to brown carbon in Beijing during winter

Organic aerosol (OA) constitutes a substantial fraction of fine particles and affects both human health and climate. It is becoming clear that OA absorbs light substantially (hence termed Brown Carbon, BrC), adding uncertainties to global aerosol radiative forcing estimations. The few current radiative-transfer and chemical-transport models that include BrC primarily consider sources from biogenic and biomass combustion. However, radiocarbon fingerprinting here clearly indicates that light-absorbing organic carbon in winter Beijing, the capital of China, is mainly due to fossil sources, which contribute the largest part to organic carbon (OC, 67 ± 3%) and its sub-constituents (water-soluble OC, WSOC: 54 ± 4%, and water-insoluble OC, WIOC: 73 ± 3%). The dual-isotope (Δ14C/δ13C) signatures, organic molecular tracers and Beijing-tailored emission inventory identify that this fossil source is primarily from coal combustion activities in winter, especially from the residential sector. Source testing on Chinese residential coal combustion provides direct evidence that intensive coal combustion could contribute to increased light-absorptivity of ambient BrC in Beijing winter. Coal combustion is an important source to BrC in regions such as northern China, especially during the winter season. Future modeling of OA radiative forcing should consider the importance of both biomass and fossil sources.

Temporal trends in classical and alternative flame retardants in bird eggs from Doñana Natural Space and surrounding areas (south-western Spain) between 1999 and 2013

Several halogenated flame retardants were detected in black kite, white stork and greater flamingo unborn eggs from Doñana Natural Space (Spain) collected in 1999, 2003, 2011 and 2013. The main components of Penta-BDE commercial mixture (BDE-47, -99 and -100) showed a decrease in the studied time interval, concurring with the ban of this mixture in the European Union (EU) in 2006. On the other hand, BDE-209, the main component of Deca-BDE mixture showed a clear trend in black kites but further monitoring is needed since its production ceased at the end of 2013. Besides, even if Dechlorane Plus (DP) was proposed by the EU as an alternative to BDE-209 no time trends were observed. Furthermore, total concentrations of PBDEs (classical FRs) are still higher than concentrations of hexabromocyclododecane (HBCD) and alternative FRs halogenated norbornenes (HNs), which are theoretically substitutes of the already banned PBDEs.

Impacts of atmospheric chlor-alkali factory emissions in surrounding populations.

Environmental exposures need to be assessed for the understanding of the health risks of general population. Organochlorine compounds (OCs) from chlor-alkali plants (CAPs) are significant for the exposomes of individuals living in locations receiving their emissions and have to be determined. The aims of the study are to identify the area of influence of past and present OC emissions from CAPs and to set quantitative body burden estimates. A CAP situated in a rural area was selected for study. The geographic distribution of the atmospheric emissions was monitored using olive tree leaves. Human biomonitoring was assessed by serum analysis from general population (n=1340). OC concentrations followed exponential decay functions with maxima in the immediate vicinity of the factory. The individuals living within 1km exhibited hexachlorobenzene (HCB), polychlorobiphenyls (PCBs) and DDT-DDE (dichlorodiphenyltrichloroethane-dichlorodiphenyldichloroethylene) concentrations that were 12, 1.3-1.9 and 3.9 times higher than in sites not influenced by the emissions from this factory. Individuals from municipalities situated 15-25km away from the CAP showed 1.5, 1.2-1.4 and 1.3 times higher serum HCB, PCB and DDT concentrations than in distant sites. The high serum concentrations of DDT and PCBs were observed even 23-31years and 9-17years after manufacture completion of these compounds, respectively. Our methodology provides a way for assessment of the influence of past and present atmospheric OCs emissions from CAPs into the exposome of individuals living in nearby areas.

Apportioned contributions of PM2.5 fine aerosol particles over the Maldives (northern Indian Ocean) from local sources vs long-range transport.

Urban-like plumes of gases and particulate matter originating from the South Asian region are frequently observed over the Indian Ocean, especially during the dry winter period. However, in addition to the strong sources on mainland South Asia, there are also local Maldivian emissions. The local contributions to the load of fine particulate matter (PM2.5) in the Maldivian capital Malé was assessed using the well-established Maldives Climate Observatory at Hanimaadhoo (MCOH) to represent local background, recording the long-range transported component for a full-year synoptic campaign at both sites in 2013. The year-round levels in both Malé and MCOH are strongly influenced by the seasonality of the monsoon cycle, including precipitation patterns and air-mass transport pathways, with lower levels during the wet summer season. The annual-average PM2.5 levels in Malé are higher (avg. 19 μg/m3) than at MCOH (avg. 13 μg/m3) with the difference being the largest during the summer, when local emissions play a larger role. The 24-h World Health Organization (WHO) PM2.5 health guideline was surpassed for the weeklong collections in 71% of the cases in Malé and in 74% of the cases for Hanimaadhoo. This study shows that in the dry/winter season 90±11% of PM2.5 levels in Malé could be from long-range transport with only 8±11% from local emissions while in the wet/monsoon season the relative contributions are about equal. The concentrations of organic carbon (OC) and elemental carbon (EC) showed similar seasonal patterns as bulk mass PM2.5. The relative contribution of total carbonaceous matter to bulk mass PM2.5 was 17% in Malé and 13% at MCOH, suggesting larger contributions from incomplete combustion practices in the Malé local region.