Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

High levels of perfluoroalkyl acids in eggs and embryo livers of great cormorant (Phalacrocorax carbo sinensis) and herring gull (Larus argentatus) from Lake Vänern, Sweden

In the eggs and developing chick livers in the two wild bird species, great cormorant and herring gull, the concentrations of a range of 15 perfluoroalkyl acids (PFAAs) were determined. Eggs of the two species were collected from Lake Vänern, Sweden, and analysed either as undeveloped egg (whole egg or separated into yolk and albumen) or incubated until start of the hatching process when the chick liver was removed and analysed. High levels of PFAAs were found in all matrixes except albumen. The predominant PFAA was perfluorooctane sulfonate (PFOS), which was found in the μg/g wet weight (ww) range in some samples of cormorant whole egg, yolk and liver and herring gull egg yolk and liver. The average concentration in yolk was 1,506 ng/g ww in cormorant and 589 ng/g ww in herring gull. The average liver concentrations of PFOS were 583 ng/g ww in cormorant and 508 ng/g ww in herring gull. At these concentrations, biochemical effects in the developing embryo or effects on embryo survival cannot be ruled out. For perfluoroalkyl carboxylates (PFCAs), the liver/egg and liver/yolk concentration ratios increased with PFCA chain length in cormorant but not in herring gull, indicating that chain length could possibly affect egg-to-liver transfer of PFCAs and that species differences may exist.     

Trace metal and metalloid levels in surface water of Marcal River before and after the Ajka red mud spill, Hungary

The aim of this study was to compare and assess the dissolved concentrations of trace elements (As, Zn, Hg, Cd, Cr, Ni, Pb and Cu) in surface water of Marcal River before and after the red mud spill that occurred in Ajka, western Hungary, in October 2010. The caustic sludge flooded the surrounding settlements and polluted the nearby Torna Creek, which flows through the Marcal and Raba rivers into the Danube. A total of 92 surface water samples were collected from the Marcal River in the period of 2007–2012 and analysed for dissolved trace metal(loid)s by atomic absorption spectroscopy method. After the spill, the water management authority initially focused on acid dosing of surface waters to lower pH and was effective in lowering both pH and metal(loid) concentrations. Among the dissolved trace metal(loid)s, arsenic and nickel levels were moderately higher in the Marcal River 2 years since the spill compared to that observed in the pre-disaster period. The concentrations of dissolved trace metal(loid)s did not exceed the European water quality standards and the US Environmental Protection Agency aquatic life criteria values (excluding one sample for cadmium).     

Mortality due to haematological cancer in cities close to petroleum refineries in Spain

Controversy exists as to whether working or living in the vicinity of a petroleum refinery (RF) increases the risk of haematological cancer (HC). The European Pollutant Release and Transfer Register obliges petroleum refineries to notify their emissions of toxic substances which include carcinogenic substances. Our objective is to determine if living in the proximity of an RF is associated with a greater risk of mortality due to HC in the census tracts (CTs) of the Spanish cities of Bilbao, Cartagena, Castellón, La Coruña, Huelva, and Santa Cruz de Tenerife. This is an ecological study of mortality in the years 1996–2007 which includes 968 CTs with 1,263,371 inhabitants. Exposure has been measured as the distance from the centroid of each CT to the RF. The Besag–York–Mollié autoregressive spatial model has been fitted by R-INLA to estimate the relative risk (RR) and 95 % credible intervals (95 % CrI) for distance in quintiles. The most distant quintile has been taken as the reference. A total of 2,574 persons died of HC. The distances from the CTs to RFs ranged from 0.5 to 22.5 km (median?=?7.6 km). All of the RRs for the quintiles of distances in Huelva were greater than 1. Statistically significant excess risk was shown in Cartagena in the nearest CT (1.8 to 6.8 km; RR?=?1.43, 95 % CrI 1.02 to 2.02). Radial effects have not been detected between the CT of residence and the petroleum RF in mortality due to HC in any of the cities.     

Trace element concentrations in soils along urbanization gradients in the city of Wien, Austria

Urban soil is an important component of urban ecosystems. This study focuses on heavy metal contamination in soils of Wien (Austria) and results are compared to those for a few large European cities. We analysed the elemental contents of 96 samples of topsoil from urban, suburban and rural areas in Wien along a dynamic (floodplain forest) and a stable (oak–hornbeam forest) urbanization gradient. The following elements were quantified using ICP-OES technique: Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Pb, P, S and Zn. For heavy metals PI (pollution index) values were used to assess the level of pollution. The PI values indicated high level of pollution by Pb in the suburban and rural area of stable gradient and in the urban area of dynamic gradient; moderate level of pollution was indicated for Cd in the urban area of stable gradient. The level of pollution was moderate for Co in the suburban and rural area of the stable gradient, and for Cu in suburban area of stable gradient, and urban area of dynamic gradient. The pollution level of Zn was moderate in all areas. Urban soils, especially in urban parks and green areas may have a direct influence on human health. Thus, the elemental analysis of soil samples is one of the best ways to study the effects of urbanization. Our results indicated that the heavy metal contamination was higher in Wien than in a few large European cities.     

Accumulation of arsenic, lead, copper, and zinc, and synthesis of phytochelatins by indigenous plants of a mining impacted area

Several native plants, able to grow in an unconfined mining impacted area that is now in close vicinity with urban areas, were evaluated for their ability to accumulate heavy metals. The main soil contaminants were As, Pb, Cu, and Zn. Sampling of the rhizospheric metal polluted soil showed that Euphorbia prostrata Aiton, Parthenium incanum Kunth, and Zinnia acerosa (DC.) A. Gray were able to grow in the presence of high amounts of mixtures of these elements. The plants accumulated the metals in the above ground parts and increased the synthesis of thiol molecules. E. prostrata showed the highest capacity for accumulation of the mixture of elements (588 μg g DW^?1). Analysis of the thiol-molecules profile showed that these plants synthesized high amounts of long-chain phytochelatins, accompanied by low amounts of monothiol molecules, which may be related to their higher resistance to As and heavy metals. The three plants showed translocation factors from roots to leaves >1 for As, Pb, Cu, and Zn. Thus, by periodically removing aerial parts, these plants could be useful for the phytoremediation of semi-arid and arid mining impacted areas, in which metal hyper-accumulator plants are not able to grow.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs)     

Phytoavailability and extractability of potassium,magnesium and manganese in calcareous soil amended with olive oil wastewater

Abstract

Land disposal of olive oil wastewater using it as a soil amendment requires a knowledge of the effects that its application may produce on the status of the mineral nutrients in the plant‐soil system. A pot experiment using calcareous soil was performed in a growth chamber to examine the effects of olive oil wastewater on the availability and postharvest soil extractability of K, Mg and Mn. The experiment included 6 treatments: two rates of olive oil wastewater, two mineral fertilizer treatments containing K (which supplied K in amounts equivalent to the K supplied by the olive oil wastewater treatments), a K‐free mineral fertilizer treatment, and a control. The pots were sown with ryegrass as the test plant, harvesting 3 times at intervals of one month. Olive oil wastewater has demonstrated a considerable capacity for supplying K that can be assimilated by the plant, tending in fact to surpass the mineral potassium fertilizer tested. The application of olive oil wastewater tends to reduce the concentration of Mg in the plant, similarly to the effect of adding mineral potassium fertilizer. An enhancement of Mn availability takes place in the soil amended with olive oil wastewater, which on occasion has produced Mn concentrations in plant that could be considered phytotoxic or at least excessive. After harvesting, we observed an increase in the amount of exchangeable K in soil with added industrial wastewater. However, these increases are lower than those in soil treated with mineral potassium fertilizer. The levels of exchangeable, carbonate‐bound, organic‐bound and residual Mg in soil were higher in treatments incorporating olive oil wastewater than in those with added mineral K, with the opposite tendency occurring in the amount of Fe‐Mn oxides‐bound Mg in soil. Treatments based on olive oil wastewater, especially in high doses, increased the amount of exchangeable and carbonate‐bound Mn in soil, in comparison with treatments adding mineral fertilizers with or without K. In contrast, the addition of industrial wastewater caused a drop in the amount of Fe‐Mn oxides‐bound and organic‐bound Mn in soil.     

Effects of synthetic pyrethroids and methidation on activities of some digestive enzymes in carp (Cyprinus carpio L.)

Abstract

The effects of pyrethroid pesticides (deltamethrin, permethrin and cypermethrin) and an organophosphate ester (methidation) on the activities of carp trypsin, α‐chymotrypsin, carboxypeptidase A and lipase were studied. The enzymes were isolated from the gastrointestinal tract and the effects of the pesticides were investigated during incubation for 5 min. The activity of trypsin was influenced only slightly by the presence of deltamethrin and methidation, whereas permethrin and cypermethrin caused significant inhibition. The pyrethroid pesticides at lower concentrations resulted in a slight activation of α‐chymotrypsin. Methidation inhibited the α‐chymotrypsin activity by about 20%. These pesticides modified the lipase activity to a lesser extent; the highest inhibition was measured with cypermethrin. The carboxypeptidase A activity was inhibited by both pyrethroid pesticides and methidation. The results suggest that these pesticides might interact with the active conformation of the studied hydrolytic enzymes, resulting in changes in their activities.     

Experimental Characterization of Atmospheric Diffusion in Complex Terrain with Land-Sea Interactions

The body of information presented in this paper is directed to scientists working in atmospheric dispersion research and model development. Two years of field measurements in the coastal area of Bilbao in northern Spain show that the diffusion behavior in this complex terrain can be classified into several well defined patterns, which correspond to certain meteorological conditions. The approach taken has been the systematic use of SO₂ remote sensors (COSPEC) and ground level monitors in moving platforms which are used to follow and document the flow of the air mass. Results to date show that complex reentry cycles can occur and that synoptically different flows may be indistinguishable by wind sensors at ground level (affected by channeling), and yet result in totally different observed pollution levels by a fixed monitoring network (affected by topographical effects). These results are being used to parameterize the cause-effect relationships and guide the modeling efforts in this area of complex terrain.