Surface ozone measurements in the southwest of the Iberian Peninsula (Huelva,Spain)

Introduction  

Photochemical ozone pollution of the lower troposphere (LT) is a very complex process involving meteorological, topographic emissions and chemical parameters. Ozone is considered the most important air pollutant in rural, suburban and industrial areas of many sites in the world since it strongly affects human health, vegetation and forest ecosystems, and its increase during the last decades has been significant. In addition, ozone is a greenhouse gas that contributes to climate change. For these reasons, it is necessary to carry out investigations that determine the behaviour of ozone at different locations. The aim of this work is to understand the levels and temporal variations of surface ozone in an industrial-urban region of the Southwest Iberian Peninsula.     

Application of the MELPUFF model to air quality assessment in the industrial area of Huelva (Spain)

The mesoscale Lagrangian puff dispersion model (MELPUFF) has been used in air quality assessment in the area of Huelva. The Huelva area is highly industrialised and it is located on the Atlantic coast of southern Spain. The MELPUFF model was applied to obtain monthly-averaged distributions of SO₂ and number of probable exceedances per month of the EU air quality standards. The study period corresponds to one year from March 1999 to February 2000. Results of monthly averaged concentrations of pollutants computed by the model were compared with the measured data at the air quality network stations.     

Organochlorine compounds in common dolphins (Delphinus delphis) from the Atlantic and Mediterranean waters of Spain

Blubber of free-ranging common dolphins (Delphinus delphis) from the northwestern coast of Spain (Atlantic), sampled in 1984 and 1996, and of common dolphins entangled in fishing nets in the southwestern Mediterranean, sampled during 1992 1994, was analysed for organochlorine pollutants. In the Atlantic, concentration of all pollutants was significantly higher in males than in females. The overall tPCB/tDDT ratio in this area was 3.35, which indicates a predominance of industrial inputs over those associated with agriculture. Individuals sampled in 1996 showed significantly lower DDT concentrations but a higher ppDDE/tDDT ratio than those sampled in 1984, which reflects the aging of the environmental load. In the same period, tPCB concentration remained constant and, as a consequence, the tPCB/tDDT ratio more than doubled. In the Mediterranean, the reduced sample size of adult individuals precluded proper statistical investigation of sex-related variation. The overall tPCB/tDDT ratio was 1.12, suggesting a higher contribution of pollutants of agricultural origin. Individuals had significantly higher levels of all DDT forms and a higher ppDDE/tDDT ratio than their counterparts from the Atlantic, but similar PCB concentrations. However, the relative frequency of the different congeners in relation to the total PCB load was different in the two areas. This indicates that the two populations do not mix, at least in the short- or medium-term. Organochlorine levels in both areas are at the mid to low end of the range of concentrations detected in other common dolphin populations and in that of other Delphinidae species from the same region. Although the impact of the organochlorine concentrations on the common dolphin populations surveyed cannot be assessed, it is considered unlikely that they have played a significant role in the decline that the species has suffered in recent decades in the western Mediterranean.     

Spatial distribution and sources of perfluorochemicals in the NW Mediterranean coastal waters (Catalonia, Spain)

This study provides the first evidence of the sources and loads of perfluorochemicals (PFCs) to the NW Mediterranean Sea. Five PFCs were analyzed in 45 seawater samples collected along the Catalan coast. Total PFCs ranged from 0.07 to 13.0 ng/l, being the levels higher in ports than in coastal waters. To determine the sources of PFCs, 8 wastewater treatment plants (WWTPs) effluents and 6 rivers discharging to the sea were also analyzed. WWTP effluents contained total PFCs levels ranging from 3.47 to 132 ng/l but due to the relatively low discharge flows, they contributed to 34.7 g/d to the sea. Total PFCs in rivers ranged from 2.24 to 21.9 ng/l and were the principal PFCs contributors to the sea. Overall, a total load of 190 g/d of PFCs are discharged to the NW Mediterranean coast. The effects and risk of PFCs discharges to the Mediterranean basin are discussed.     

Trends in the elemental composition of fine particulate matter in Santiago, Chile, from 1998 to 2003

Santiago, Chile, is one of the most polluted cities in South America. As a response, over the past 15 yr, numerous pollution reduction programs have been implemented by the environmental authority, Comisión Nacional del Medio Ambiente. This paper assesses the effectiveness of these interventions by examining the trends of fine particulate matter (PM(2.5)) and its associated elements. Daily fine particle filter samples were collected in Santiago at a downtown location from April 1998 through March 2003. Additionally, meteorological variables were measured continuously. Annual average concentrations of PM(2.5) decreased only marginally, from 41.8 microg/m3 for the 1998-1999 period to 35.4 microg/m3 for the 2002-2003 period. PM(2.5) concentrations exceeded the annual U.S. Environmental Protection Agency standard of 15 microg/m3. Also, approximately 20% of the daily samples exceeded the old standard of 65 microg/m3, whereas approximately half of the samples exceeded the new standard of 35 microg/m3 (effective in 2006). Mean PM(2.5) levels measured during the cold season (April through September) were three times higher than those measured in the warm season (October through March). Particulate mass and elemental concentration trends were investigated using regression models, controlling for year, month, weekday, wind speed, temperature, and relative humidity. The results showed significant decreases for Pb, Br, and S concentrations and minor but still significant decreases for Ni, Al, Si, Ca, and Fe. The larger decreases were associated with specific remediation policies implemented, including the removal of lead from gasoline, the reduction of sulfur levels in diesel fuel, and the introduction of natural gas. These results suggest that the pollution reduction programs, especially the ones related to transport, have been effective in reducing various important components of PM(2.5). However, particle mass and other associated element levels remain high, and it is thus imperative to continue the efforts to improve air quality, particularly focusing on industrial sources.     

Evaluation of Organochlorine Compounds (PCDDs,PCDFs, PCBs and DDTs) in Two Raptor Species Inhabiting a Mediterranean Island in Spain (8 pp)

Background Species that are at high levels of the food web have often been used as bioindicators to evaluate the presence of persistent contaminants in ecosystems. Most of these species are long-lived, so pollutant burdens may be integrated in some complex way over time. This makes them particularly sensitive to deleterious effects of Persistent Organic Pollutants (POPs). Birds have been suggested as useful organisms for monitoring pollutant levels. Traditionally such studies have been carried out with raptors such as osprey (Pandion haliaetus), peregrine falcon (Falco peregrinus), bald eagle (Haliaetus leucocephalus), etc. In this paper we present the results of a monitoring study conducted on two raptor species, osprey (Pandion haliaetus) and red kite (Milvus milvus), inhabiting a Mediterranean island (Menorca, Spain). These two species have different feeding habits; ospreys prey on fish and red kites feed on terrestrial species. This study constitutes a good opportunity to investigate if differences in feeding habits (aquatic vs. terrestrial) influences the contaminants pattern in two species inhabiting the same area. Methods The study was conducted in a non-destructive way, using only failed eggs, to avoid the damage of the population stability. Eggs were collected during the period 1994–2000. The contaminants examined were dichlorodiphenyltrichloroethanes (DDTs, including DDT and its main metabolite, DDE), polychlorinated biphenyls (PCBs), including ortho PCBs (PCBs with at least one Chlorine atom in the ortho position): #28, 52, 95, 101, 123+149, 118, 114, 153, 132+105, 138, 167, 156, 157, 180, 170, 189, 194; and non ortho PCBs (PCBs with no Chlorine atom in the ortho position): #77, 126, 169 and all the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) with Chlorine atoms at the 2,3,7 and 8 position (2,3,7,8-substituted PCDDs and PCDFs). The analysis of organochlorine compounds was performed using a sample treatment based on a Solid Phase Matrix Dispersion procedure. Ortho PCBs and DDTs were determined by HRGC-μECD; non ortho PCBs and PCDD/Fs were determined by HRGC-HRMS. Results and Discussion The sum of the ortho PCB congeners analysed ranged from 0.94 to 15.03 μg/g wet weight (ww) for ospreys and from 1.0 to 11.2 μg/g ww for red kites. In both species, PCB congeners #153, #138 and #180 accounted about 75% to total ortho PCB concentrations. Regarding non ortho PCBs, for ospreys, concentrations ranged from 0.16 to 1.39 ng/g wet weight (ww) and for red kites from 0.12 to 0.51 ng/g ww, being congener #126 the most abundant. Concerning DDTs, concentration for ospreys ranged from 0.07 to 1.03 μg/g ww; and for red kites ranged from 0.90 to 2.10 μg/g ww, representing DDE more than 95% of the total DDTs, which proves a past use of DDT in the study area. Differences in contaminant levels between species are probably associated to feeding habits. The fish-eating species presents the highest PCB levels, whereas the terrestrial species exhibits the highest DDT levels. PCDD/Fs in ospreys were in the range 2.6–14.2 pg/g ww, while in red kites the range was slightly wider (22.2–43.2 pg/g ww), being PCDDs the major contributors in black kites. Ospreys had PCDDs similar to PCDF concentrations. PCDD/F profiles were mostly influenced by OCDD in both species. Non ortho PCBs were the major contributors to calculated Toxic Equivalent Quantity (TEQs) in both species. Conclusion In both species studied, ortho-PCBs could represent a problem of concern since 57% of the eggs exhibited levels higher than 4 μg/g ww, reported as the level that could cause reduced hatchability, embryo mortality, and deformities in birds. Recommendations and Outlook Results found in this study suggest that a more detailed study to clear up possible deleterious effects of PCBs on the bird populations studied here should be done. Section Editor: Prof. Dr. Paola Gramatica (paola.gramatica@uninsubria.it)     

Analysis of lipid peroxidation in animal and plant tissues as field-based biomarker in Mediterranean irrigated agroecosystems (Extremadura,Spain)

ABSTRACT

The development of field-based biomarkers can allow for a more reliable assessment of the exposure of organisms to pollutants. Different sampling sites, along two streams running through an irrigable agricultural area, were selected to evaluate the effect of agrochemical load on the measured endpoints. The levels of lipid peroxidation were evaluated in several organs of Procambarus clarkii. The same method was applied to leaves of two woody species. Determining levels of MDA (malonaldehyde) by thiobarbituric acid reactive substances assay allows measuring the levels of lipid peroxidation. Differences in lipid peroxidation levels were observed in P. clarkii individuals collected at different sites; however, the patterns varied depending on the organ (when accounting for variations due to sex). The use of a MDA-gills/MDA-hepatopancreas index allowed for discrimination between reference and polluted sites. Significant differences in oxidative damage between sites were found in the leaves of Quercus rotundifolia but not in Salix sp. The lipid peroxidation of crayfish organs and holm oak leaves as a suitable biomarker of environmental pollution deserves further investigation.     

Characterization of the Atlanta area aerosol,elemental composition and possible sources

This paper presents a study or the elemental characterization of the Atlanta area aerosol at one rural and several urban sites. It includes a determination of the concentrations of major elemental components of the aerosol and a statistical analysis of the relationships between these components as a means of investigating possible sources. This research has emphasized the study of the graphitic carbon, C_e, and elemental sulfur, S, components of the aerosol (these two components are important in visibility reduction studies). The measurements show that C_e and S represent, respectively 3.1–9.9% and 1.9–4.4% of the total suspended paniculate, TSP, mass. The concentrations of C_e, S and TSP exhibit strong seasonal variations with C_e decreasing from winter to summer and S and TSP increasing over this period. All elemental components exhibit less concentration at the rural site than at the urban sites. Analysis results show that C_e appears to be statistically separate from S, which is assumed to be present as sulfate, indicating that the sources for C_e and particulate sulfate are distinct. S and TSP, however, appear to be linked through common regional scale meteorological processes.     

Spatial and seasonal variations of elemental composition in Mt. Everest (Qomolangma) snow/firn

In May 2005, a total of 14 surface snow (0–10 cm) samples were collected along the climbing route from the advanced base camp to the summit (6500–8844 m a.s.l.) on the northern slope of Mt. Everest (Qomolangma). A 108 m firn/ice core was retrieved from the col of the East Rongbuk Glacier (28.03°N, 86.96°E, 6518 m a.s.l.) on the north eastern saddle of Mt. Everest in September 2002. Surface snow and the upper 3.5 m firn samples from the core were analyzed for major and trace elements by inductively coupled plasma mass spectroscopy (ICP-MS). Measurements show that crustal elements dominated both surface snow and the firn core, suggesting that Everest snow chemistry is mainly influenced by crustal aerosols from local rock or prevalent spring dust storms over southern/central Asia.There are no clear trends for element variations with elevation due to local crustal aerosol inputs or redistribution of surface snow by strong winds during the spring. Seasonal variability in snow/firn elements show that high elemental concentrations occur during the non-monsoon season and low values during the monsoon season. Ca, Cr, Cs, and Sr display the most distinct seasonal variations. Elemental concentrations (especially for heavy metals) at Mt. Everest are comparable with polar sites, generally lower than in suburban areas, and far lower than in large cities. This indicates that anthropogenic activities and heavy metal pollution have little effect on the Mt. Everest atmospheric environment. Everest firn core REE concentrations are the first reported in the region and seem to be comparable with those measured in modern and Last Glacial Maximum snow/ice samples from Greenland and Antarctica, and with precipitation samples from Japan and the East China Sea. This suggests that REE concentrations measured at Everest are representative of the background atmospheric environment.     

Assessing the effects of tertiary treated wastewater reuse on the presence emerging contaminants in a Mediterranean river (Llobregat,NE Spain)

Purpose  

The Llobregat River, which is characterized by important fluctuations of the flow rates, receives treated waters from WWTPs. During the years 2007 and 2008, the Llobregat River basin suffered from a severe drought which affected the supply of drinking water facilities (DWF) that rely on the exploitation of the river water. The Catalan Water Agency implemented a water reuse experiment with the objective of maintaining the river flow rate at sufficiently high level so as to ensure the supply of raw water to Barcelona’s major DWF.     

Comparing the response of biochemical indicators (biomarkers) and biological indices to diagnose the ecological impact of an oil spillage in a Mediterranean river (NE Catalunya, Spain)

Three biomarkers of hydrocarbon exposure, liver 7-ethoxyresourfin-O-deethylase activity (EROD), fluorescent hydrocarbon compounds (FACs) in bilis, and the liver antioxidant enzyme catalase (CAT) were examined in the autochthonous fish species Barbus meridionalis collected in the river Fluvià (NE Catalunya, Spain) after an oil spillage. Four different locations were sampled, including the impacted site, upstream and downstream sites and a reference site. Biomarker responses were compared with diatom and macroinvertebrate community assemblage metrics (Specific Pollution Sensitivity index - IPS, and Iberian Biological Monitoring Working Party - IBMWP, respectively). Chemical analyses denoted that polycyclic aromatic hydrocarbon levels in sediment were much higher at the impacted site than in downstream reaches. Four fold increase of EROD activity together with increased levels of biliary FACs in barbs collected at the spilled site indicated exposure of inhabiting fish to the oil. Additionally, CAT activity was significantly depressed (four fold) when compared to other stations, thus suggesting that fish collected from the impacted sites could be more susceptible to suffer oxidative stress. Biological indices (particularly that of the diatom community IPS) showed slight significant effects between control and impacted sites, indicating that more tolerant taxa were favoured because of the oil spillage. These results support the need to include biochemical responses measured in local species in monitoring programmes aimed to diagnose specific pollution effects in stressed river ecosystems.     

Assessing decadal changes in rainwater alkalinity at a rural Mediterranean site in the Montseny Mountains (NE Spain)

Annual volume-weighted mean (VWM) concentrations in rainwater collected at La Castanya (LC, Montseny Mountains, NE Spain) were analysed from 1983 to 2000 to study the temporal trends in precipitation chemistry, and the causes behind the changes. A significant positive correlation was found between annual rainwater SO₄²⁻ concentrations at LC and Spanish SO₂ emissions (r=0.73, P=0.0008) both decreasing remarkably during this period. Rainwater alkalinity increased during the period, shifting from negative values at the beginning (VWM in the 5 initial years=−2.7 μeq l⁻¹) to alkaline values in recent years (VWM in the 5 final years=18.0 μeq l⁻¹). Stepwise regression analysis indicated that 88% of the variation of alkalinity could be accounted for by the variability of non-marine Ca²⁺ and non-marine SO₄²⁻, with a more prominent dependence on Ca²⁺.Rains of African provenance were highly enriched in alkalinity and Ca²⁺, but no significant increases in their occurrence were found for the study period. Because of the reported higher dust updraft in northern Africa during years of high North Atlantic Oscillation (NAO) index, we also explored the relationship between rainwater variables associated with an African provenance and NAO. Annual precipitation was inversely related to NAO (r=−0.61, P=0.007). The annual wet deposition of African dust-related elements showed no correlation with NAO, probably because wet deposition of these elements depends on two factors (precipitation and dust updraft) which have opposite behaviour with respect to NAO. We hypothesise that dry deposition of African dust during dry spells (not sampled in this study) might be higher during high NAO-index years.     

Polychlorinated biphenyls in two mollusc species from the coast of Tenerife (Canary Islands, Spain)

Levels of PCBs were determined in two marine organisms, limpets (Patella ullisiponensis aspera) and winkles (Ossilinus atratus), sampled in three stations in the south east coast of Tenerife during 1993. Winkles and limpets exhibited different PCB patterns. Principal Component Analysis (PCA) was used to study the patterns and the relationships among PCBs.     

Impact assessment of a large river on the sediments and fish from its continental shelf: using Solea solea as sentinel in the Ebro river mouth (NW Mediterranean,Spain)

Environmental Science and Pollution Research - Many studies have been carried out along mighty rivers with heavily industrialized watersheds to evaluate pollutants and their effects on freshwater...     

Organochlorinated pesticides in sediments from the Lake Albufera of Valencia (Spain)

Bottom sediment samples from 121 sites of the Lake Albufera of Valencia were analyzed. Dieldrin, endrin, heptachlor and op′-DDT were not detected (<0.01 ng g⁻¹) in 88–93% of the sites. Aldrin and HCB concentration ranges were between <0.01 and 0.1 ng g⁻¹ in 86% and 94% of the sites, respectively. Heptachlor-epoxide and lindane 95% confidence intervals were 0.2–0.5 and 0.06–0.12, respectively. The greatest average concentration corresponds to pp′-DDE, pp′-DDD and pp′-DDT. The sum of six isomers and derivatives of the DDT average concentration reaches 2.1 ng g⁻¹, as opposed to 2.7 ng g⁻¹ for the sum of 13 pesticides considered. In the site with a major contamination, 27.0 ng g⁻¹ of pp′-DDD and 12.8 ng g⁻¹ of pp′-DDT were accumulated. The DDE:DDT proportion average was 0.37, indicating an aged DDT contamination. Concentrations of pesticides in sediments were compared to three sediment quality guidelines, and indicated that a low biological effects level can be expected in either sediments or aquatic organisms.     

Presence of plutonium contamination in soils from Palomares (Spain)

More than 30 years after the occurrence of an aircraft accident which involved the detonation of two nuclear weapons in the surrounding area of the village of Palomares (Spain), the affected terrestrial area has been investigated for remaining transuranic contamination. Evidence from the presence of this contamination was initially found through the analysis of the 241Am inventories in superficial soil samples collected in the region, and was confirmed through the analysis of the (239+240)Pu inventories and their associated 238Pu/(239+240)Pu activity ratios in the same samples. However, it was also observed that a considerable fraction of the remaining contamination in the area was present in particulate form, i.e. as "hot particles". The work performed in our laboratory for identification, isolation and characterisation of these "hot particles" as well as some conclusions obtained from these analyses are outlined in this paper.     

Concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk of women from Catalonia, Spain

In this study, the concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain, were determined. The study was performed after 4 years of regular operations in the facility and the present PCB levels were compared with baseline concentrations obtained in a pre-operational program. PCBs and PBDEs levels were determined by HRGC/HRMS in 15 samples. In the present study planar PCBs ranged from 1.3 to 6.3 pg WHO-TEQ/g fat with a mean value of 3.8 pg WHO-TEQ/g fat. After adding dioxin-like mono-ortho-PCBs the total PCB-TEQ concentrations ranged from 3.8 to 13.3 pg WHO-TEQ/g fat (mean value: 8.7 pg WHO-TEQ/g fat). A comparison of the current data with those obtained in the baseline study showed significant decreases for both planar and total WHO-TEQ of PCBs: 47.9% and 44.6%, respectively. PCB concentrations in milk of women living in urban zones were higher than those living near industrial areas (10.1 and 7.4 pg WHO-TEQ/g fat, respectively). Mean PBDE concentrations were 2.2 and 2.5 ng/g fat for women living in urban and industrial zones, respectively. Dietary intake of PCBs and PBDEs for a standard adult woman samples were 898 and 843 ng/day for PCBs, and 72 and 63 ng/day for PBDEs, for residents in urban and industrials areas, respectively. This study suggests that dietary intake is more relevant for human exposure to PCBs and PBDEs than living near the HWI.     

Impact of elevated CO(2) and nitrogen fertilization on foliar elemental composition in a short rotation poplar plantation

The experiment was carried out on a short rotation coppice culture of poplars (POP-EUROFACE, Central Italy), growing in a free air carbon dioxide enriched atmosphere (FACE). The specific objective of this work was to study whether elevated CO(2) and fertilization (two CO(2) treatments, elevated CO(2) and control, two N fertilization treatments, fertilized and unfertilized), as well as the interaction between treatments caused an unbalanced nutritional status of leaves in three poplar species (P. x euramericana, P. nigra and P. alba). Finally, we discuss the ecological implications of a possible change in foliar nutrients concentration. CO(2) enrichment reduced foliar nitrogen and increased the concentration of magnesium; whereas nitrogen fertilization had opposite effects on leaf nitrogen and magnesium concentrations. Moreover, the interaction between elevated CO(2) and N fertilization amplified some element unbalances such as the K/N-ratio.