Eduardo D. Wannaz

Atmospheric quality and distribution of heavy metals in Argentina employing Tillandsia capillaris as a biomonitor

The atmospheric quality and distribution of heavy metals were evaluated throughout a wide region of Argentina. In addition, the biomonitor performance of Tillandsia capillaris Ruiz & Pav. f. capillaris was studied in relation to the accumulation of heavy metals and to its physiologic response to air pollutants. A sampling area of 50,000 km2 was selected in the central region of the Argentine Republic. This area was subdivided into grids of 25 x 25 km. Pools of T. capillaris, where present, were collected at each intersection point. From each pool three sub-samples were analyzed independently. Furthermore, five replicates were collected at 20% of the points in order to analyze the variability within the site. The content of Co, Cu, Fe, Ni, Mn, Pb and Zn was determined by Atomic Absorption Spectrometry. Chemical-physiological parameters were also determined to detect symptoms of foliar damage. Chlorophylls, phaeophytins, hydroperoxy conjugated dienes, malondialdehyde and sulfur were quantified in T. capillaris. Some of these parameters were used to calculate a foliar damage index. Data sets were evaluated by one-way ANOVA, correlation analysis, principal component analysis and mapping. Geographical distribution patterns were obtained for the different metals reflecting the contribution of natural and anthropogenic emission sources. According to our results it can be inferred that Fe, Mn and Co probably originated in the soil. For Pb, the highest values were found in the mountainous area, which can be attributed to the presence of Pb in the granitic rocks. Ni showed mainly an anthropogenic origin, with higher values found in places next to industrial centers. For Zn the highest values were in areas of agricultural development. The same was observed for Cu, whose presence could be related to the employment of pesticides. The foliar damage index distribution map showed that the central and southeastern zones were the ones where the major damage in the bioindicator was found. The central zone coincides with the city of Córdoba whereas the southeastern area is strictly agricultural, so the high values found there could be related to the use of pesticides.

Assessment of human health risk related to metals by the use of biomonitors in the province of Córdoba, Argentina.

The evaluation of metal contents in the environment is of vital importance for the assessment of human exposure. Thus the species Usnea amblyoclada, Ramalina celastri and Tillandsia capillaris were tested as bioaccumulators of transition metals in the urban area of Córdoba city, Argentina. The level of metals on biomonitors was compared to that of total deposition samples. All three species discriminated zones within the urban area of Córdoba city with different pollution levels; they revealed high levels of Zn in the downtown area and confirmed high levels of some transition metals in an industrial area. The correlation analysis revealed that the lichen R. celastri had the highest correlation rates with total deposition samples, suggesting it is a valuable biomonitor of atmospheric pollution. A significant relationship was also observed between respiratory diseases in children and the contents of metal accumulated in R. celastri and T. capillaris, indicating their usefulness when assessing human exposure to metals.

Distribution of atmospheric trace elements and assesment of air quality in Argentina employing the lichen, Ramalina celastri, as a passive biomonitor: detection of air pollution emission sources

Ramalina celastri was used as a passive biomonitor to study the relationship between elemental accumulation, emission sources and physiochemical parameters used as air pollution biomarkers in Argentina. The concentration of 27 elements was determined in the thalli by Neutron Activation Analysis (NAA). The content of photosynthetic pigments, peroxidation products, water and sulphur was determined and a Pollution Index (PI) was calculated. Factor analysis was used to locate the possible emission sources of elements. Overall, the elemental concentrations were similar to other biomonitoring studies. The higher levels of arsenic were related to the soil particulate matter, which is characteristically rich in this element. High uranium concentrations were found near a uranium mine and levated levels of zinc were found in areas congested with heavy traffic. Although there is no direct relationship found between the physiological parameters and the elemental concentrations, the geographical distribution of the PI allowed to detect areas with increased lichen damage.

Integral assessment of pollution in the Suquía River (Córdoba, Argentina) as a contribution to lotic ecosystem restoration programs.

The Suquía River lower-middle basin (Córdoba, Argentina) is subject to a strong anthropic impact because it receives pollutants from different sources (industries, wastewaters, heavy traffic, agricultural land use, etc.) We have assessed the degree of watershed degradation of Suquía River lower-middle sections through the analysis of different ecosystem compartments (air, water, riparian soil, sediments and biota), in order to provide useful data to be considered in future river restoration programs. Four study sites were selected along the river (La Calera city, Córdoba city, Corazón de María village and Río Primero city) which were sampled during the low- and high-water flow periods. We analyzed: a) chemical and physical characteristics of water, sediments, and riparian soil; b) heavy metal content of water and sediments, and c) semi-volatile organic compounds in air. Besides, pollutant bioindicators such as fish assemblages, lichens (Usnea amblyoclada), vascular plants (Tradescantia pallida), and microorganisms (fecal coliform and Escherichia coli) were used to further assess the status of the river. All analyzed ecological compartments were affected by water pollution, particularly, fish assemblages, sediments and riparian soils by heavy metal and coliform bacteria. Moreover, we detected a possible contribution of sulfur and a high pollutant content in air that merit further research about other air-water exchanges. Accordingly, we strongly suggest that an action to restore or remediate the anthropic effect on the Suquía River be extended to all possible compartments along the river.

Air pollutants effect on monoterpenes composition and foliar chemical parameters in Schinus areira L.

Monoterpenes, pigments, lipid peroxidation products, sulfur and water content expressed as dry weight/fresh weight ratio were measured in leaves of Schinus areira L. collected in Mendoza, Argentina. The sampling sites showed different SO(2), NO(2) and PM(10) levels, which allowed setting out zones by mapping. Foliar chemical parameters in S. areira were analysed in relation to these zones. High hydroperoxy conjugated dienes (HPCD) and alpha-phellandrene content in foliar samples coming from areas with high SO(2) levels were measured. Principal component analysis (PCA) showed a positive association among SO(2), HPCD, malondialdehyde, sabinene and beta-pinene. In relation to NO(2) levels high values of chlorophyll (Chl)-b and Chl-b/Chl-a ratio were found. PCA showed for NO(2), an association with Chl-b/Chl-a, phaeophytin-a/Chl-a ratios and alpha-phellandrene. As regard PM(10), no significant differences were found in the chemical parameters indicating foliar damage, whereas the contents of tricyclene, alpha-pinene and beta-pinene showed low values in the area with high levels of this pollutant. From the results, it can be inferred that the more noticeable changes in the foliar chemistry of S. areira were detected in relation to the different SO(2) levels. This response was associated to an increase in the foliar oxidation processes accompanied by modifications in the levels of terpenes. This is important, as SO(2) was the only pollutant whose values in the annual arithmetic mean were over the standard value of 30 ppb.

Identification of atmospheric trace-element sources by passive biomonitoring employing PCA and variogram analysis

The epiphyte plant Tillandsia capillaris was used as a passive biomonitor to study the relationship between elemental accumulation and emission sources in the province of Córdoba, Argentina. The concentrations of As, Ba, Br, Ca, Ce, Co, Cr, Cs, Eu, Fe, Gd, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Se, Sm, Ta, Tb, Th, U, Yb, and Zn were determined in T. capillaris leaves by Instrumental Neutron Activation Analysis. A variogram analysis was performed to identify the emission sources of these elements in the study area, obtaining different patterns for each element analysed. A principal-component analysis was subsequently performed to further confirm the different contaminant emission sources and it coincided with the results of the variogram analysis. We observed that the enrichment of most elements was associated with natural sources (soil) and that only some elements showed evidence of enrichement related to sources such as traffic (K, Sb and Zn), industries (Br), and mining activity (Ca).

Accumulation of Aluminium and Physiological Status of Tree Foliage in the Vicinity of a Large Aluminium Smelter

A pollution gradient was observed in tree foliage sampled in the vicinity of a large aluminium production facility in Patagonia (Argentina). Leaves of Eucalyptus rostrata, and Populus hybridus and different needle ages of Pinus spec. were collected and concentrations of aluminium (Al) and sulphur (S) as well as physiological parameters (chlorophyll and lipid oxidation products) were analyzed. Al and S concentrations indicate a steep pollution gradient in the study showing a relationship with the physiological parameters in particular membrane lipid oxidation products. The present study confirms that aluminium smelting results in high Al and sulphur deposition in the study area, and therefore further studies should be carried out taking into account potentially adverse effects of these compounds on human and ecosystem health.

Suitability of Tillandsia usneoides and Aechmea fasciata for biomonitoring toxic elements under tropical seasonal climate.

Aechmea fasciata was evaluated for the first time as a biomonitor of toxic elements, in comparison to the biomonitoring capacity of Tillandsia usneoides, a well-established biomonitor bromeliad species. Plants of both species were exposed to air pollutants from industrial, urban, and agricultural sources, under the tropical seasonal climate, from June/2011 to April/2013, in five sites of São Paulo State, Brazil, for 8 consecutive exposure periods of 12 weeks each. The levels of essential and non-essential elements, including trace metals, were quantified at the end of each exposure. T. usneoides and A. fasciata indicated N, Fe, Zn, Co, Cr, and V as air contaminants in the studied sites, during wet and dry seasons and both species were recommended for qualitative biomonitoring. Concentration levels of N, Ca, S, Fe, Zn, Cu, B, Co, and Ni were significantly higher in T. usneoides than in A. fasciata. However, A. fasciata showed a higher effective retention capacity of Ni, Pb, V, Cu, Fe, Cr, and Co during field exposure, as indicated by the estimate of enrichment factor relative to basal concentrations. This species is more suitable for detecting the atmospheric pollution level of those metals than the T. usneoides. Both species indicated adequately the seasonal differences in the pollution levels of several elements, but T. usneoides presented higher ability for biomonitoring the spatial variations and for indicating more properly the sources of each element in the studied region than the A. fasciata.

Relationship between trace elemental composition in Fraxinus pennsylvanica bark and the incidence of some respiratory diseases in Córdoba, Argentina

In order to evaluate the use of Fraxinus pennsylvanica as a biomonitor of trace elements and to investigate their relationship with the incidence of some respiratory diseases in children, bark samples of F. pennsylvanica were collected at ten sampling sites near healthcare centres in Cordoba city, Argentina, and analysed by Total Reflection X-ray Fluorescence with synchrotron radiation. Factor analysis was used to identify element emission sources. The first factor was associated with industrial activities, the second might represent soil sources and the third factor was related to vehicular traffic emissions. Pearsons correlation analysis between these factors and the incidence of respiratory diseases showed that factor 1 correlated with allergic rush, factor 2 with allergic rhinitis and factor 3 with respiratory infections. The results suggest that bark samples of F. pennsylvanica can be use as an efficient biomonitor to assess the human exposure to trace elements.

Elemental composition of PM 2.5 in the urban environment of San Juan, Argentina

This study contributes to the current knowledge about air pollution in the province of San Juan, Argentina. Sampling was carried out to measure the fine particulate matter in the atmosphere (PM2.5) of the city of San Juan. PM2.5 was collected continuously during the winter and spring seasons of 2014 and 2015, and the concentrations of 14 elements (Pb, Ca, K, Cd, Ni, Cr, Mn, V, Cu, Ti, Ba, Co, Sr, and Fe) were determined in PM2.5 filters using the technique of X-ray fluorescence by synchrotron radiation (SR-XRF). The results revealed that PM2.5 presented annual and seasonal variations, showing a higher concentration during the winter seasons. In addition, for the elements quantified in the filters, a multivariate analysis (Positive Matrix Factorization) was performed to identify the main sources of emission of these elements in the study area, with a series of components being obtained that corresponded to their compositions, which were assigned physical meanings. The first factor, which was the most important in contribution of the sum of the measured elements (45%), was determined mainly by the elements K, Ti, V, Mn, and Fe, which came predominantly from soil particles. The second factor contributed 30% to the measured species in PM2.5, with higher Ba and Zn content perhaps being related to emissions from vehicular traffic. Finally, the third factor, in which Pb, Cr, and Ca predominated, may be an indicator of industrial activity and contributed 25% of the sum of the measured elements of PM2.5. The results of this study provide the first PM composition database in the province, and this can now be used in the development of mitigation and prevention programs.