Contribution of Mine-Derived Airborne Particulate Matter to Ca, Fe, Mn and S Content and Distribution in the Lichen Punctelia hypoleucites Transplanted to Bajo de la Alumbrera Mine, Catamarca (Argentina).

The aim of this work was to relate the contribution of mine-derived airborne particulate matter to Ca, Fe, Mn and S content and distribution in Punctelia hypoleucites transplanted to Bajo de la Alumbrera, an important open-pit mine in Catamarca, Argentina. Lichen samples were transplanted to four monitoring sites: two sites inside the mine perimeter and two sites outside the mine. After three months, elemental distribution in samples was analyzed by microparticle-induced X-ray emission (microPIXE), and elemental concentration was determined by specific techniques: Ca and Fe by instrumental neutron activation analysis, Mn by inductively coupled plasma atomic emission spectrometry and S by a turbidimetric method. A differential distribution of S and Ca in thalli transplanted in-mine sites was detected compared to that of samples transplanted outside-mine sites. An overlap of Fe and S in the upper cortex of the apothecium section was observed, leading to infer a mineral association of both elements. Similar association was observed for Ca and S. In addition to these results, the significantly higher concentration detected for S and Mn in in-mine site samples suggests a contribution of Fe, S, Ca and Mn of mining origin to the content and distribution of these elements in P. hypoleucites. MicroPIXE complemented with Mössbauer spectroscopy analysis determined the presence of pyrite particles together with other iron-bearing minerals displaying different degrees of oxidation. These results point to a mining origin of the airborne particulate matter trapped by the lichen thalli transplanted to Bajo de la Alumbrera. These findings indicate that P. Hypoleucites acts as an excellent air quality biomonitor in the Bajo de la Alumbrera mine area.

A multi-analytical approach to studying the chemical composition of typical carbon sink samples.

Peatlands in southern South America (Tierra del Fuego region, TdF) play a key role in the ecological dynamics of Patagonia. It is, therefore, necessary to increase our knowledge and awareness of their scientific and ecological value to ensure their conservation. This study aimed to assess the differences in the distribution and accumulation of elements in peat deposits and Sphagnum moss from the TdF. Chemical and morphological characterization of the samples was carried out using various analytical techniques, and total levels of 53 elements were determined. Furthermore, a chemometric differentiation based on the elemental content of peat and moss samples was performed. Some elements (Cs, Hf, K, Li, Mn, Na, Pb, Rb, Si, Sn, Ti and Zn) showed significantly higher contents in moss samples than in peat samples. In contrast, only Mo, S and Zr were significantly higher in peat samples than in moss samples. The results obtained highlight the ability of moss to accumulate elements and to act as a means to facilitate the entry of elements into peat samples. The valuable data obtained in this multi-methodological baseline survey can be used for more effective conservation of biodiversity and preservation of the ecosystem services of the TdF.

Implementing the monitoring breakdown structure: native lichens as biomonitors of element deposition in the southern Patagonian forest connected with the Puyehue volcano event in 2011-a 6-year survey (2006-2012).

This study aims to investigate the airborne elements' deposition by using native Usnea barbata lichens as biomonitors in the forested areas of Tierra del Fuego (TdF, southern Patagonia), an apparently pristine environment. The present study is linked to the volcanic eruption of the Puyehue-Cordón Caulle which started in north Patagonia in June 2011, which gives rise to long-distance transport of pollutants through the atmosphere at 1700 km from our sampling sites. The monitoring breakdown structure (MBS) was applied to three sampling campaigns in 2006 (baseline) âž” 2011-2012 (3 and 15 months after the volcanic event, respectively). We have on purpose enhanced the information variety endowment: (i) Seventy-one referenced sites were double sampled; (ii) up to 426 composite lichen samples were collected; (iii) twenty-six elements were measured by neutron activation analysis (As, Ba, Br, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Rb, Sb, Sc, Se, Sm, Ta, Tb, Th, U, Yb, Zn) for samples of 2011 and 2012 campaigns; (iv) thirteen common elements (As, Ba, Ca, Co, Cr, Cs, Fe, K, Na, Sb, Se, U, Zn) were determined in 2006 for the baseline comparison. The natural contamination by tephras is reflected by lichens more clearly in the 2011 campaign, where Ba, Cr, Na, Ca, Cs, and U showed higher median levels compared with the baseline campaign (2006). Ca, K, and Na were the most accumulated elements after the volcano event and could be associated with the volcanic ashes' deposition. Rare earth elements (REEs) showed no significant bioaccumulation levels between 2011 and 2012, indicating their association with higher lithogenic inputs than volcanic ashes. Using the Earth's crust as reference, nine elements (As, Ba, Br, Ca, K, Na, Sb, Se, and Zn) presented moderate/significant mean enrichment factor (EF) values (> 5). The usefulness of Usnea barbata as test species for direct biomonitoring oriented kinetic studies in areas characterized by a low human impact is confirmed. Eventually, our results confirm that TdF is not an actual pristine environment as earlier supposed.

Physiological Response and Multi-Elemental Content in Lichens Growing on Agricultural Fences: A Pilot Study Comparing No-Tillage and Organic Cropping.

The objective of this study is to compare the physiological response (content and degradation of photosynthetic pigments, membrane oxidation products and soluble proteins) and multi-element content of Ramalina celastri (lichenized fungi) growing on agricultural fences with no-tillage (associated with transgenic crops and agrochemical application), organic cropping and a non-cultivated area. We found that R. celastri did not differ in its physiological response to agricultural practices, except for the contents of chlorophyll b and phaeophytin a which were high in both cultivated areas. Lichens growing in organic cropping fields have higher arsenic, chromium, uranium and internal transition elements common in the earth's crust, possibly due to the greater resuspension of the material during soil tillage. Lichens that grow on posts close to no-tillage field had higher bromine contents (present in numerous pesticides). We found evidence that R. celastri behaves as a tolerant species to air pollution in agricultural environments.

Trace elements deposition in the Tierra del Fuego region (south Patagonia) by using lichen transplants after the Puyehue-Cordón Caulle (north Patagonia) volcanic eruption in 2011.

Lichen Usnea barbata transplants were tested as a biomonitor of atmospheric deposition in an apparently pristine environment that is Tierra del Fuego region (Patagonia, Argentina). The present survey is connected with the volcanic eruption that started in north Patagonia on June 4, 2011 from the Puyehue-Cordón Caulle volcano, Chile (north Patagonia, at 1700 km of distance of our sampling sites). Lichens were collected in September 2011 (one month of exposure) and September 2012 (1 year of exposure) in 27 sites covering the northern region of the province where trees are not present. The atmospheric deposition of 27 elements by using Neutron Activation Analysis (NAA) was determined in the collected samples. The first aim of the study was to evaluate the influence of the volcanic eruption on the regional atmospheric deposition comparing our results with baseline data we determined in U. barbata in 2006 in the same sites. The second aim was to test possible patterns of bioaccumulation between the two sampling campaigns after the volcanic eruption. With respect to 2006 baseline levels, we found significant higher levels for As, Ba, Co, Cr, Cs, Na, Sb and U in lichens collected after 1 month of exposure (first sampling campaign--2011). Between the two sampling campaigns (2011-2012) after the eruption, lichens reflected the natural contamination by volcanic ashes with significantly higher median levels of Br, Cr, Fe, K, Na, Sc, and Se. Results confirmed the very good aptitude of U. barbata to reflect the levels of elements in the environment at global scale and to reflect the volcanic emissions at distant places. Volcanic eruptions cause the emission in the atmosphere of elevated levels of particulate matter. In this regard, our findings demonstrate the importance to evaluate the metal composition of the particles to avoid possible health effects.

Heavy metals and trace elements in atmospheric fall-out: their relationship with topsoil and wheat element composition.

The objectives of this study were to determine the average concentrations and deposition rates of 28 elements in atmospheric bulk deposition and to elucidate associations among topsoil, bulk deposition and wheat element composition. The fluxes of arsenic (As), copper (Cu), lead (Pb) and zinc (Zn) deposition in Córdoba were higher than in other agro-ecosystems, which reflects both natural (geochemistry and topsoil removal) and anthropogenic sources. High lanthanide, uranium (U) and thorium (Th) concentrations revealed the impact of an open cast uranium mine. The highest enrichment factors (EF) were those of Cu, Pb, Zn and nickel (Ni), with calcium (Ca) being the most prominent in the surroundings of a cement plant. Industries and the transport of airborne urban pollutants were the main anthropogenic sources for Ca, Cu, Ni, Pb, Zn, cadmium (Cd), iron (Fe), manganese (Mn) and antimony (Sb). The concentrations of metals in wheat grain were predicted using the topsoil and atmospheric fall-out composition with R(2)=0.90, with the latter being the best explanatory variable. The present study highlights the potential health hazards of wheat consumption (Environmental Protection Agency) by the assessment of heavy metals in bulk atmospheric deposition.

Heavy metal and trace element concentrations in wheat grains: assessment of potential non-carcinogenic health hazard through their consumption.

Heavy metal and trace element concentrations were examined in wheat grains and straw to elucidate associations between air pollution sources and soil variables. The mean wheat grain concentrations of Cr, Cu, Fe, Mn and Zn surpassed the tolerance limits stated in the international legislation for wheat grain and foodstuffs. When topsoil Ba, Co, Cr and Zn concentrations were higher than the legislation thresholds for agricultural and residential soils, wheat grain concentrations were also increased. In addition, Cr, Cu, Mn, Ni, Pb, and Zn revealed an immobilization effect of a cement plant and the atmospheric deposition input, with Cd in wheat grains being associated with a cement plant and industrial waste incinerator. The health risks arising from wheat grain consumption indicated that the inhabitants of Argentina are experiencing significant non-carcinogenic risks (Hazard Index = 3.311), especially when consuming wheat grains affected by metallurgical or chemical factories, as well as by air transportation from big cities.

Heavy metal pollution in topsoils near a cement plant: the role of organic matter and distance to the source to predict total and hcl-extracted heavy metal concentrations.

Heavy metal and trace element concentrations were examined in topsoils to evaluate a cement plant and an industrial waste incinerator as pollution sources. As, Ba, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Se, Sm, Ta, Tb, Th, U, Yb and Zn were measured by Neutron Activation Analysis (NAA), and Co, Cu, Fe, Ni, Pb and Zn by a 0.5M-hydrochloric extraction technique using an Atomic Absorption Spectrophotometer (AAS). The Cr total concentration and HCl-extracted Co and Mn were possibly related to wind transportation from an industrial area in the north of Córdoba city (Argentina). Cu, Pb and Zn in partial HCl extraction were influenced by the cement plant and the industrial area in the north of Córdoba city. The mean total Ba concentration was above the residential and agricultural land use limits stated in national and international legislation and was related to the distance to the cement plant. The concentrations of HCl-extracted heavy metals could be predicted by the organic matter percentage and the distance to the cement plant (with R(2) values of 0.50-0.74). The Ca total concentration was seen to have little influence whereas the organic matter percentage strongly affected HCl-extracted heavy metals according to the correlation analysis and multiple regression models. According to soil quality guidelines for environmental health, the human and wildlife populations in Yocsina might be experiencing toxic Ba and Cr effects.