Industrial sources are among the least documented PM (Particulate Matter) source in terms of chemical composition, which limits our understanding of their effective impact on ambient PM ...concentrations. We report 4 chemical emission profiles of PM2.5 for multiple activities located in a vast metallurgical complex. Emissions profiles were calculated as the difference of species concentrations between an upwind and a downwind site normalized by the absolute PM2.5 enrichment between both sites. We characterized the PM2.5 emissions profiles of the industrial activities related to the cast iron (complex 1) and the iron ore conversion processes (complex 2), as well as 2 storage areas: a blast furnace slag area (complex 3) and an ore terminal (complex 4). PM2.5 major fractions (Organic Carbon (OC) and Elemental Carbon (EC), major ions), organic markers as well as metals/trace elements are reported for the 4 industrial complexes. Among the trace elements, iron is the most emitted for the complex 1 (146.0 mg g−1 of PM2.5), the complex 2 (70.07 mg g−1) and the complex 3 (124.4 mg g−1) followed by Al, Mn and Zn. A strong emission of Polycyclic Aromatic Hydrocarbons (PAH), representing 1.3% of the Organic Matter (OM), is observed for the iron ore transformation complex (complex 2) which merges the activities of coke and iron sinter production and the blast furnace processes. In addition to unsubstituted PAHs, sulfur containing PAHs (SPAHs) are also significantly emitted (between 0.011 and 0.068 mg g−1) by the complex 2 and could become very useful organic markers of steel industry activities. For the complexes 1 and 2 (cast iron and iron ore converters), a strong fraction of sulfate ranging from 0.284 to 0.336 g g−1) and only partially neutralized by ammonium, is observed indicating that sulfates, if not directly emitted by the industrial activity, are formed very quickly in the plume. Emission from complex 4 (Ore terminal) are characterized by high contribution of Al (125.7 mg g−1 of PM2.5) but also, in a lesser extent, of Fe, Mn, Ti and Zn. We also highlighted high contribution of calcium ranging from 0.123 to 0.558 g g−1 for all of the industrial complexes under study. Since calcium is also widely used as a proxy of the dust contributions in source apportionment studies, our results suggest that this assumption should be reexamined in environments impacted by industrial emissions.
Schematic representation of the method used to determinate the industrial profiles using downwind and upwind sites: A) Side view, B) overhead view. Display omitted
•Exhaustive PM2.5 chemical profiles emitted by steelworks subunits are investigated.•Sulfate is emitted by the oxygen converter process but also by combustion processes.•PAHs and sulfur containing PAH are emitted by combustion processes.•Calcium is emitted by all subunits but differences are obtained for Ca/Ca2+ ratios.•Al, Fe, Zn, Mn, Ti are emitted by all subunits, proportion dependent of processes.
The bioaccumulation of metals (As, Cd, Co, Cr, Cu, Ni, Pb, Sb, V, Zn, Al, Fe) and organochlorine compounds (PCDD-Fs and PCBs) was assessed in soils and vegetables of 3 sites of contrasted ...anthropogenic influence (rural and industrial-urban areas). Cultivated soils in industrial areas exhibited diffuse pollution in organochlorine pollutants (PCBs and PCDD-Fs). The pollutant levels encountered in vegetables were always lower than the EU regulatory or recommended values. However, the contents measured in vegetables cultivated near industrialized areas were significantly higher than those observed in rural areas. This was notably the case for Co, Cd, Cr, Ni, Pb, V, NDL- and DL-PCB, PCDD, and PCDF. The leaf pathway appeared as the main absorption pathway for many contaminants. The results suggested that population exposure to pollutants was mainly caused by vegetable ingestion. In the vegetables and soils, the toxicity was mainly caused by the V, Co, Cd, and Pb contents to which can be added As and PCDD-Fs for soils. Therefore, the proximity of vegetable crops to highly anthropised areas has led to long-term exposure of vegetables and soils to air pollutants, leading to an accumulation in the food chain and thus a risk for human health.
A study to characterize primary particulate matter (PM
2.5 and PM
10) from the French vehicular fleet was conducted during winter 2008, in a tunnel in Marseille, France. The carbonaceous fraction ...represents 70% of the aerosol mass and elemental carbon fraction (EC) represent 60% of the carbonaceous fraction. The organic carbon OC was characterized in term of its water soluble fraction, functionalization rate and HULIS content. Seventy trace organic compounds including alkanes, polycyclic aromatic hydrocarbons (PAH), petroleum biomarkers and carboxylic acids were also quantified, in order to determine an organic emission profile for chemical mass balance modeling studies. Such source profiles were still missing in Europe and particularly in France. The profile obtained in this study is consistent with profiles determined in tunnel or dynamometer studies performed in other countries during the last ten years. These results suggest that organic compounds profiles from vehicular exhaust emissions are not significantly influenced by the geographic area and are thus suitable for use in aerosol source apportionment modeling applied across extensive regions. The chemical profile determined here is very similar to those obtained for diesel emissions with high concentrations of EC relative to OC (EC/OC = 1.8) and low concentrations of the higher molecular weight PAH. These results are consistent with the high proportion of diesel vehicles in the French fleet (49%).
The removal of chloride, nitrate and sulfate ions from aqueous solutions by a macroporous resin is studied through the ion exchange systems OH⁻/Cl⁻, OH⁻/NO₃ ⁻, OH⁻/SO₄ ²⁻, and HCO₃ ⁻/Cl⁻, Cl⁻/NO₃ ⁻, ...Cl⁻/SO₄ ²⁻. They are investigated by means of Langmuir, Freundlich, Dubinin-Radushkevitch (D-R) and Dubinin-Astakhov (D-A) single-component adsorption isotherms. The sorption parameters and the fitting of the models are determined by nonlinear regression and discussed. The Langmuir model provides a fair estimation of the sorption capacity whatever the system under study, on the contrary to Freundlich and D-R models. The adsorption energies deduced from Dubinin and Langmuir isotherms are in good agreement, and the surface parameter of the D-A isotherm appears consistent. All models agree on the order of affinity OH⁻<HCO₃ ⁻<Cl⁻<NO₃ ⁻<SO₄ ²⁻, and distinguish high energy processes (OH⁻/Cl⁻, OH⁻/NO₃ ⁻, OH⁻/SO₄ ²⁻, Cl⁻/SO₄ ²⁻) from lower energy systems (HCO₃ ⁻/Cl⁻, Cl⁻/NO₃ ⁻). The D-A and D-R models provide the best fit to the experimental points, indicating that the micropore volume filling theory is the best representation of the ion exchange processes under study among other adsorption isotherms. The nonlinear regression results are also compared with linear regressions. While the parameter values are not affected, the evaluation of the best fitting model is biased by linearization.
The removal of chloride, nitrate and sulfate ions from aqueous solutions by a macroporous resin is studied through the ion exchange systems OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), and ...HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-), Cl(-)/SO(4)(2-). They are investigated by means of Langmuir, Freundlich, Dubinin-Radushkevitch (D-R) and Dubinin-Astakhov (D-A) single-component adsorption isotherms. The sorption parameters and the fitting of the models are determined by nonlinear regression and discussed. The Langmuir model provides a fair estimation of the sorption capacity whatever the system under study, on the contrary to Freundlich and D-R models. The adsorption energies deduced from Dubinin and Langmuir isotherms are in good agreement, and the surface parameter of the D-A isotherm appears consistent. All models agree on the order of affinity OH(-)<HCO(3)(-)<Cl(-)<NO(3)(-)<SO(4)(2-), and distinguish high energy processes (OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), Cl(-)/SO(4)(2-)) from lower energy systems (HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-)). The D-A and D-R models provide the best fit to the experimental points, indicating that the micropore volume filling theory is the best representation of the ion exchange processes under study among other adsorption isotherms. The nonlinear regression results are also compared with linear regressions. While the parameter values are not affected, the evaluation of the best fitting model is biased by linearization.
Although banned for years, organochlorine pesticides and PCBs continue to affect aquatic life, dolphins being particularly exposed. The concentrations of 31 PCB congeners, and 15 banned pesticides or ...metabolites were measured in 5 tissues of 68 striped dolphins stranded in the Northwestern Mediterranean coast in 2010–16. The results were compared to historical data (1988–2009) and, even though there is a slow decreasing trend, the levels in the 2010–2016 samples were still elevated based on common cetacean toxicological thresholds. A transition period in 2007–08, probably caused by a morbillivirus epizootic amplified the stranding, espacially of highly contaminated specimens. From 2010, higher proportions in parent compounds towards metabolites were observed yet again. These changing patterns were likely reflect the exposure of dolphins to the remobilization of pollutants from contaminated soils and sediments, with a prominent role of rivers. This should lead to an even slower decline of these contaminants that could last for decades, requiring new efforts to reduce their dispersal to aquatic ecosystems.
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•Banned organochlorine contaminants globally decreased in dolphins since 1988.•Global levels remain elevated and still constitute a threat to dolphins.•Levels of parent compounds towards metabolites reflect a shift in contaminants origin.•Increasing parent compounds suggest diffusion from contaminated lands and sediment.•Morbillivirus epizootic likely affected preferably highly multi-contaminated dolphins.
There are few cetacean tissue-specific polycyclic aromatic hydrocarbon (PAH) concentration studies in the Mediterranean, despite this region is among the most subjected to chemical contamination. PAH ...analyses were conducted in different tissues of striped dolphins (Stenella coeruleoalba, N = 64) and bottlenose dolphins (Tursiops truncatus, N = 9) stranded along the French Mediterranean coastline from 2010 to 2016. Comparable levels were measured in S. coeruleoalba and T. trucantus (1020 and 981 ng g−1 lipid weight in blubber, 228 and 238 ng g−1 dry weight in muscle, respectively). The results suggested a slight effect of maternal transfer. The greatest levels were recorded by urban and industrial centers, and decreasing temporal trends were observed in males muscle and kidney, but not in other tissues. As a conclusion, the elevated levels measured could represent a serious threat to dolphins populations in this region, particularly by urban and industrial centers.
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•PAH were elevated in Stenella coeruleoalba and Tursiops truncatus.•Lower levels in S. coeruleoalba females suggest little maternal transfer.•Naphthalene, fluorene, 5- and 6-rings PAHs dominated in all tissues.•Highest levels were localized by urban and industrial areas.•Constant time trends in blubber and liver, possibly decreasing in muscle and kidney.
The removal of chloride, nitrate, and sulfate ions from wastewaters by a macroporous ion-exchange resin is studied through the experimental results obtained for six ion exchange systems, OH(-)/Cl(-), ...OH(-)/NO3(-), OH(-)/SO4(2-), and HCO3(-)/Cl(-), Cl(-)/NO3(-), Cl(-)/SO4(2-). The results are described through thermodynamic modeling, considering either an ideal or a nonideal behavior of the ionic species in the liquid and solid phases. The nonidealities are determined by the Davies equation and Wilson equations in the liquid and solid phases, respectively. The results show that the resin has a strong affinity for all the target ions, and the order of affinity obtained is OH(-) < HCO3(-) < Cl(-) < NO3(-) < SO4(2-). The calculation of the changes in standard Gibbs free energies (ΔG(0)) shows that even though HCO3(-) has a lower affinity to the resin, it may affect the removal of Cl(-), and in the same way that Cl(-) may affect the removal of NO3(-) and SO4(2-). The application of nonidealities in the thermodynamic model leads to an improved fit of the model to the experimental data with average relative deviations below 1.5% except for the OH(-)/SO4(2-) system. On the other hand, considering ideal or nonideal behaviors has no significant impact on the determination of the selectivity coefficients. The thermodynamic modeling is also compared with the Dubinin-Astakhov adsorption isotherms obtained for the same ion exchange systems. Surprisingly, the latter performs significantly better than the ideal thermodynamic model and nearly as well as the nonideal thermodynamic model.
The bioaccumulation of PAHs and metal elements in the indigenous lichens Xanthoria parietina was monitored during two years at a quarterly frequency, in 3 sites of contrasted anthropic influence. The ...impact of the meteorological factors (temperature, relative humidity, rainfall, wind speed) was first estimated through principal component analysis, and then by stepwise multilinear regressions to include wind directions. The pollutants levels reflected the proximity of atmospheric emissions, in particular from a large industrial harbor. High humidity and mild temperatures, and in a lower extent low wind speed and rainfall, also favored higher concentration levels. The contributions of these meteorological aspects became minor when including wind direction, especially when approaching major emission sources. The bioaccumulation integration time towards meteorological variations was on a seasonal basis (1–2 months) but the wind direction and thus local emissions also relied on a longer time scale (12 months). This showed that the contribution of meteorological conditions may be prevalent in remote places, while secondary in polluted areas, and should be definitely taken into account regarding long-term lichen biomonitoring and inter-annual comparisons. In the same time, a quadruple sampling in each site revealed a high homogeneity among supporting tree species and topography. The resulting uncertainty, including sampling, preparation and analysis was below 30% when comfortable analytical conditions were achieved. Finally, the occurrence of unexpected events such as a major forest fire, permitted to evaluate that this type of short, although intense, events did not have a strong influence on PAH and metals bioaccumulation by lichen.
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•N and C stable isotopes provided intraspecific and fine spatial resolution information.•Several metals were found higher in fish nearby corresponding industrial release.•PAH ...bioaccumulation occurred through water incorporation and was driven by metabolism.•Forbidden pesticides decline was observed in Conger conger.•European conger fits most of the bioindication requirements when >100 cm.
To evaluate the capacity of the European conger (Conger conger) as a reliable bioindicator to investigate marine contaminant sources and pathways, the muscles of 24 individuals caught in a semi-enclosed industrialized bay (Gulf of Fos, France) were analyzed for numerous organic compounds, metal elements, and stable isotopes. The contaminant levels were elevated to moderate, which relates to the great anthropic pressure from the surrounding industries and maritime traffic. Stable isotope analyses finely discriminated between three geographical areas and between two age groups. Mercury (Hg) and arsenic (As) concentrations (nd-1.35 mg.kg−1 and 5.94–60.1 mg.kg−1wet weight (ww), respectively), as well as chlorination by-products, were elevated in particular areas, identifying specific industrial sources. Levels of Σ42PCB (7.15–28.67 µg.kg−1ww), Σ16PAH (3.64–9.48 µg.kg−1ww) and Σ10pesticides (1.91–18.42 µg.kg−1ww) in fish muscles, as expected, did not differ among sites.
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