Distribution of volatile organic compounds in Madrid (Spain)

From November 1995 to October 1996, airborne concentrations of VOCs were measured in the Madrid area to study the organic pollution in general, and the correlation between different pollutants in relation to such parameters as location and season. Mean concentrations for up to 90 compounds were measured at four test sites, including both urban and suburban areas. At the urban sites, maximum concentrations occurred in the autumn and winter, whereas minimum concentrations were reached in summer and spring. Similar changes were obtained for the lesscontaminated site located in the SE of the city, whereas a different pattern was found at the site in the NW of the city due to meteorological aspects. Mean levels of hydrocarbons in Madrid were quite similar to those found in other European cities. Chemometrical techniques were applied to the set of data in order to assess the influence of such factors as traffic, temperature and seasonal variations on the VOC levels.     

Diurnal variability of total ozone column over Madrid (Spain)

In recent years, research on ozone variability has mainly focused on the analysis of its trend. Additionally some studies have analyzed the annual, seasonal and day-to-day ozone variations. However, intra-diurnal total ozone variations are notably less explored. Thus, the main objective of this paper is to analyze the diurnal variability of total ozone column (TOC) as recorded by a Brewer spectrophotometer in Madrid (Spain). The results show that about 90% of days present non-negligible diurnal variability, indicating that, in general, it should not be assumed that TOC remains constant throughout a particular day in urban areas. In addition, this variability has a notable seasonal behavior which should be considered (the spring and summer months show higher diurnal TOC variations than autumn and winter months). This pattern is likely caused by the diurnal photochemical processes in the lower troposphere related to the formation of tropospheric ozone near the earth’s surface at populated urban locations. Thus, these diurnal fluctuations in tropospheric ozone could explain part of diurnal TOC variations (between 20% and 70% depending on the mixing layer height).     

Lead levels of feral pigeons (Columba livia) from Madrid (Spain)

Tissue lead data are presented for populations of feral pigeons (Columba livia) from three locations in Madrid (Spain). The lead present in the lungs and digestive tract of pigeons increased progressively with traffic density and in parallel with atmospheric and ground lead values. The contribution of the respiratory route of Pb intake to the pigeons was about three times greater than the digestive route. The highest Pb values were found in bones. It is suggested that the pigeons gave a greatly magnified picture of lead pollution in cities than indicated by atmospheric lead concentrations.     

Modelling the influence of peri-urban trees in the air quality of Madrid region (Spain)

Tropospheric ozone (O(3)) is considered one of the most important air pollutants affecting human health. The role of peri-urban vegetation in modifying O(3) concentrations has been analyzed in the Madrid region (Spain) using the V200603par-rc1 version of the CHIMERE air quality model. The 3.7 version of the MM5 meteorological model was used to provide meteorological input data to the CHIMERE. The emissions were derived from the EMEP database for 2003. Land use data and the stomatal conductance model included in CHIMERE were modified according to the latest information available for the study area. Two cases were considered for the period April-September 2003: (1) actual land use and (2) a fictitious scenario where El Pardo peri-urban forest was converted to bare-soil. The results show that El Pardo forest constitutes a sink of O(3) since removing this green area increased O(3) levels over the modified area and over down-wind surrounding areas.     

Measurements of selected PCBs in open urban ambient air of Madrid (Spain)

The focus of this study was to characterize the concentration levels of selected PCBs and compare them to compiled data in order to contribute to the international database. The sampling site is located in the outskirts of Madrid and can be considered an open urban area. 32 samples of air were taken from February 1998 to June 1998 by using a high volume air sampler. Glass fiber filters and polyurethane foam (PUF) were used to collect the paniculate and gas phase material, respectively. PUF plugs were Soxhlet extracted and filters were ultrasonically extracted by using pesticide-grade hexane and dichloromethane, respectively. The cleanup procedure was carried out on a florisil column with hexane and hexane/dichloromethane as elution solvents. GC/MS in a selected ion monitoring mode was used for quantification and 29 selected PCBs congeners were analyzed.     

Modelling of the migration of trace elements along groundwater flowpaths by using a steady state approach application to the site at El Berrocal (Spain)

The applications of geochemical modelling to natural water systems mostly rely upon the equilibrium assumption. This is in principle justified for deep groundwater systems with long water residence times.In addition, trace element behaviour in these natural systems has been normally modelled by taking into account the precipitation and dissolution of individual trace element phases.Recent geochemical modelling work related to natural analogue systems would indicate that: (1) the equilibrium condition is restricted to a limited number of components in long water residence times and (2) the behaviour of trace metals is very much connected to the major component cycling in the system.There is a need to develop our geochemical modelling capabilities to take these two facts into account in order to be able to predict the behaviour of trace components (radionuclides) in a geological repository.In this work we report on the successful application of steady-state kinetics in conjunction with co-dissolution/co-precipitation approaches to model trace element geochemistry in the natural analogue system at El Berrocal. The evolution of major components of the system (Ca (II), Al (III), CO₃²⁻ and Si) as well the trace elements investigated (U, Ba and Mn) is well reproduced by using the coupling between steady-state kinetics and co-dissolution/co-precipitation approaches.     

Biomonitoring of trace metals in a mine-polluted estuarine system (Spain)

In this paper, we examine metal concentrations in the water and in the crustacean Balanus balanoides from the Huelva estuary, one of the most polluted estuaries in Europe. Metal levels in waters are very high, especially those of Zn, Fe and Cu. Zn presents the highest concentrations, with a mean value of 690 microg l-1 in 2001 and 301 microg l-1 in 2002. As the water flows down through the estuary toward the sea, the metal concentrations drop sharply and the pH rises. The metal concentrations in balanoides tissues are, in general, very high, undoubtedly due to the high metal pollution of the water where it lives. Metal concentrations in Balanus balanoides tissues behave similarly to those in the water, reaching maximums in the upper part of the estuary and diminishing as we approach the sea. The element that reaches the highest levels in Balanus balanoides is Zn, with a mean value of 54.6 g kg-1 in 2001 and 29.9 g kg-1 in 2002, followed by Cu and Fe. There is a significant correlation (p<0.01) for concentrations of Cd, Cu, Fe, Mn, Ni and Zn in Balanus balanoides relative to their concentration in waters. Barnacles showed a great capacity to accumulate metals, especially Zn, Cu and Fe. Based on the results obtained, we can conclude that Balanus balanoides is a good tool for monitoring trace metals in the Huelva estuary.     

Exposure to trace elements of flamingos living in a biosphere reserve, the Camargue (France)

Recent research has shown that some adult flamingos Phoenicopterus roseus collected from the Camargue Biosphere Reserve had tissue metal concentrations considerably higher than the average for this species. As the range of these birds is large, the origin of the contamination was unknown. Blood and feather samples from nestling flamingos were therefore analysed for trace metals to determine the presence and origin of local contamination. A comparison of elemental concentration in the feathers of nestling and adult flamingos revealed higher concentrations of Cd, Cu, Pb and Se in adults, and higher concentrations of Zn in juveniles. This was attributed to increased exposure to atmospheric pollutants of adults, and either differences in Zn requirements and metabolism between adults and juveniles, or a local contamination of the juveniles' food supply by Zn. Concentrations of Zn in serum were also very elevated compared with human standards. Cd, Cu, Zn and Se concentrations were analysed in outer (O) and inner (I) barbs (i.e. barbs that are, respectively, exposed or not exposed to external deposits) of greater coverts of nestling flamingos. A comparison of elemental concentrations in these two feather components indicates a local atmospheric contamination by Cd, Cu and Pb.     

A model for evaluation of the phytoavailability of trace elements to vegetables under the field conditions

Currently, several single extraction methods are used for the evaluation of the phytoavailability of metals using pot experiments. A systematic comparison, however, is lacking. It is especially true for the field studies. This study was to investigate the phytoavailability of trace elements to vegetables grown on metal-contaminated soils under the field conditions. All soils collected were typical calcareous soils in northern China. Four frequently used methods using CaCl2, diethylenetriaminepentaacetic acid (DTPA), CH3COOH, and water as extractants were compared for phyto-availability. The concentrations of metals extracted by these four extraction methods ranged from 3.42 to 815, 1.51- 6965, 0.732-24473, 0.688-7863, 0.246-685, 1.99-5337 0.203-4649 ng/g for Cr, Ni, Zn, Cu, Cd, Pb and REEs, respectively. Simple correlation analysis indicated that a significant correlation (Cr: r = 0.5411**; Zn: r = 0.6352**; Cd: r = 0.6979**; Pb: r = 0.5537** and REEs: r = 0.5185** -0.6684**) was observed between the CaCl2-extractable metals in soil solution and that in Chinese cabbage. In addition, soil pH, organic matter (OM), and cation exchange capacity (CEC) also affect the phytoavailability. An empirical model was developed to express the combined effect of soil properties on the phytoavailability. The stepwise multiple regression analysis demonstrated that the phytoavailability of trace elements strongly correlated with the extractable fraction by CaCl2, total metal concentration in soils, and soil pH, OM, CEC. This model can describe approximately 75-95% of the variability of metal uptake and the r2 values ranged from 0.741** to 0.954**, which were much better than the single correlation analysis. For celery and cole, a strong correlation was obtained for Cr, Ni, Zn, Cu, Cd, La, Ce, Pr and Nd. For spinach and Chinese cabbage, however, a positive correlation was only observed for 1 and 3 metals, respectively. Generally, the developed empirical model can integrate the combined effects of soil properties, extractable metal fractions in soil solutions and plant species on the phytoavailability of metals to vegetables in the field conditions.     

Anthropogenic and natural influence on the PM(10) and PM(2.5) aerosol in Madrid (Spain). Analysis of high concentration episodes

Non-mineral carbon is the main component of PM10 and PM2.5 at an urban roadside site in Madrid accounting for more than 50% of the total bulk mass in winter pollution episodes. In these cases a 70-80% of the particle mass is anthropogenic. Particles of crustal/mineral origin contribute significantly to the observed PM10 concentrations, especially in spring and summer. They have also been found in the PM2.5 fraction although secondary particles are the next most important contributor in this size. Long-range transport particle episodes of Saharan dust significantly contribute to exceedence of the new daily limiting PM10 value in the urban network and at nearby rural background stations. This type of long-range transport event also influences PM2.5 concentrations. The crustal contribution can account for up to 67 and 53% of the PM10 and PM2.5 bulk mass in such cases.     

Mercury, lead and cadmium in human milk in relation to diet, lifestyle habits and sociodemographic variables in Madrid (Spain)

Background

Although breastfeeding is the ideal way of nurturing infants, it can be a source of exposure to toxicants. This study reports the concentration of Hg, Pb and Cd in breast milk from a sample of women drawn from the general population of the Madrid Region, and explores the association between metal levels and socio-demographic factors, lifestyle habits, diet and environmental exposures, including tobacco smoke, exposure at home and occupational exposures.

Methods

Breast milk was obtained from 100 women (20 mL) at around the third week postpartum. Pb, Cd and Hg levels were determined using Atomic Absorption Spectrometry. Metal levels were log-transformed due to non-normal distribution. Their association with the variables collected by questionnaire was assessed using linear regression models. Separate models were fitted for Hg, Pb and Cd, using univariate linear regression in a first step. Secondly, multivariate linear regression models were adjusted introducing potential confounders specific for each metal. Finally, a test for trend was performed in order to evaluate possible dose-response relationships between metal levels and changes in variables categories.

Results

Geometric mean Hg, Pb and Cd content in milk were 0.53 μg L⁻¹, 15.56 μg L⁻¹, and 1.31 μg L⁻¹, respectively. Decreases in Hg levels in older women and in those with a previous history of pregnancies and lactations suggested clearance of this metal over lifetime, though differences were not statistically significant, probably due to limited sample size. Lead concentrations increased with greater exposure to motor vehicle traffic and higher potato consumption. Increased Cd levels were associated with type of lactation and tended to increase with tobacco smoking.

Conclusions

Surveillance for the presence of heavy metals in human milk is needed. Smoking and dietary habits are the main factors linked to heavy metal levels in breast milk. Our results reinforce the need to strengthen national food safety programs and to further promote avoidance of unhealthy behaviors such as smoking during pregnancy.     

Low molecular weight thiols in arsenic hyperaccumulator Pteris vittata upon exposure to arsenic and other trace elements

Low molecular weight thiol-containing compounds have been reported to play an important role in metal detoxification and accumulation in some higher plants. The formation of these low molecular weight thiols in the recently discovered arsenic hyperaccumulator, Chinese Brake fern (Pteris vittata) upon exposure to arsenic and other trace metals was investigated. In addition to cysteine and glutathione, an unidentified thiol was observed in the plants exposed to arsenic, which was not found in the control. The concentration of the unidentified thiol showed a very strong and positive correlation with arsenic concentration in the leaflets. The unidentified thiol was low in rachises and undetectable in the roots for As-treated plants. Total and acid-soluble thiols were also measured and the results indicated that arsenic mainly stimulated the synthesis of acid-soluble thiol in Chinese Brake. The investigations of other trace elements (Cd, Cu, Cr, Zn, Pb, Hg, and Se) showed that these elements were not accumulated in Chinese Brake to high levels and the synthesis of the unidentified thiol in the plant was not observed. Our study suggests that the unidentified thiol was induced specifically by arsenic and the distribution patterns of the unidentified thiol and arsenic in the plant were consistent, indicating that the synthesis of this compound was related to As exposure.     

Levels of PCDDs, PCDFs and non-ortho PCBs in serum samples of non-exposed individuals living in Madrid (Spain)

In an attempt to evaluate the background levels of PCDDs, PCDFs and non-ortho PCBs in people living in Madrid (Spain), blood serum samples had been analyzed PCDD, PCDF and coplanar PCB levels from non exposed individuals are reported in this study. Average levels found were 515.29 ppt for total PCDDs, 66.73 ppt for total PCDFs and 85.47 ppt for non-ortho PCBs on a lipid weight basis Calculated I-TEQ values were 8.78 ppt for PCDDs, 6.96 for PCDFs and 7.03 for coplanar PCBs on a lipid weight basis.     

Determination of trace elements and evaluation of their enrichment factors in Himalayan lichens

Within the framework of the Ev-K2-CNR research program of the Italian National Research Council a specific task project has been initiated for the identification of trace elements in lichens in remote high altitude areas. This is to evaluate the possibility of using lichens as biomonitors of trace elements of atmospheric pollution. In this preliminary study, more than 20 elements have been determined in some species of lichens collected at different altitudes (from 1300 to 5000 m) in the region of the Sagarmatha National Park (Nepal). Samples of superficial soils were also collected and analyzed to calculate the trace element enrichment factors (EF) using scandium as a normalizing element. Most of the trace elements were determined by instrumental neutron activation analysis (INAA), while lead and cadmium measurements were carried out with electrothermal atomic absorption spectroscopy (ET-AAS). The EF values as well as the elemental concentrations are reported and discussed.     

Analytical improvements of hybrid LC-MS/MS techniques for the efficient evaluation of emerging contaminants in river waters: a case study of the Henares River (Madrid, Spain)

Purpose  

Instrumental capabilities and software tools of modern hybrid mass spectrometry (MS) instruments such as high-resolution mass spectrometry (HRMS), quadrupole time-of-flight (QTOF), and quadrupole linear ion trap (QLIT) were experimentally investigated for the study of emerging contaminants in Henares River water samples.     

Profile of trace elements in Parasol Mushroom (Macrolepiota procera) from Tucholskie Forest

The aim of this study was to determine 19 elements contents and bioconcentration potential in fruiting bodies of Parasol Mushroom (Macrolepiota procera) collected from the Tucholskie Forest complex in Poland. Also discussed were Cd, Pb and Hg contents of edible caps in relation to the current regulatory standards. K, P and Mg were particularly abundant in caps and stipes, median values were 38-49, 13, and 1.6-1.6 mg/g dry weight, and followed by Ca, Na and Rb at 110-540, 44-240 and 20-50 μg/g dw, respectively. Concentrations of Al, Fe, Zn, Cu and Mn were from less than 50 to 180 μg/g dw, while concentrations of other elements were ～l.0?μg/g dw or less. Cu, K, Ag, Cd, Na, Rb, Zn and Hg were bioconcentrated (BCF >1), while Al, Ba, Fe, Mn, Co, Sr, Pb and Cr were not bioaccumulated (BCF <1). Cd and Pb content of Parasol Mushroom's edible caps collected from some sites in the Tucholskie Forest exceed the maximum levels set in the EU for cultivated mushrooms.     

Chemical fingerprinting applied to the evaluation of marine oil pollution in the coasts of Canary Islands (Spain)

Chemical fingerprinting approach to environmental assessment is illustrated in the evaluation of marine oil pollution in the coasts using two limpet species as bioindicator organisms, and based on profiles and concentrations of n-alkanes and aromatic hydrocarbons in their tissues. Accidental and chronic releases of hydrocarbons can contaminate the marine environment of the Canary Islands not only because of their geographical situation but also because of the very dense tanker traffic around. This situation affects coastal areas, fishing activities, tourism resort, etc. Concentrations of n-alkanes and aromatic hydrocarbons (polycyclic aromatic hydrocarbons and methyl-polycyclic aromatic hydrocarbons) in the soft tissues of the marine intertidal and subtidal limpets, Patella crenata and Patella ullysiponensis aspera, were evaluated. Limpet samples were collected at monthly intervals, at three locations on the southeast coast of Tenerife over a 3-year period (1991-93). Levels of hydrocarbons found in limpets are similar to concentrations found in unpolluted areas around the world. From application of principal component analysis, the interpretation of variable loading plots gives information on variable correlation and can be used to distinguish among potential sources of pollution and the ability of studied molluscs to be used as bioindicator organisms.     

Source origin of trace elements in PM from regional background,urban and industrial sites of Spain

Despite their significant role in source apportionment analysis, studies dedicated to the identification of tracer elements of emission sources of atmospheric particulate matter based on air quality data are relatively scarce. The studies describing tracer elements of specific sources currently available in the literature mostly focus on emissions from traffic or large-scale combustion processes (e.g. power plants), but not on specific industrial processes. Furthermore, marker elements are not usually determined at receptor sites, but during emission. In our study, trace element concentrations in PM₁₀ and PM_2.5 were determined at 33 monitoring stations in Spain throughout the period 1995–2006. Industrial emissions from different forms of metallurgy (steel, stainless steel, copper, zinc), ceramic and petrochemical industries were evaluated. Results obtained at sites with no significant industrial development allowed us to define usual concentration ranges for a number of trace elements in rural and urban background environments. At industrial and traffic hotspots, average trace metal concentrations were highest, exceeding rural background levels by even one order of magnitude in the cases of Cr, Mn, Cu, Zn, As, Sn, W, V, Ni, Cs and Pb. Steel production emissions were linked to high levels of Cr, Mn, Ni, Zn, Mo, Cd, Se and Sn (and probably Pb). Copper metallurgy areas showed high levels of As, Bi, Ga and Cu. Zinc metallurgy was characterised by high levels of Zn and Cd. Glazed ceramic production areas were linked to high levels of Zn, As, Se, Zr, Cs, Tl, Li, Co and Pb. High levels of Ni and V (in association) were tracers of petrochemical plants and/or fuel-oil combustion. At one site under the influence of heavy vessel traffic these elements could be considered tracers (although not exclusively) of shipping emissions. Levels of Zn–Ba and Cu–Sb were relatively high in urban areas when compared with industrialised regions due to tyre and brake abrasion, respectively.     

The abundances of rarer trace elements in paddy (rice) soils of Sri Lanka

Concentrations of Ti, Ga, As, Sc, Zr, Sn, Hf, Th, U and Y have been determined for 70 paddy soils from 14 villages, selected throughout Sri Lanka by means of ICP-MS. The mean elemental contents of all paddy soil samples were 6120 Ti, 14.1 Ga, 0.84 As, 7.26 Sc, 129 Zr, 2.27 Sn, 3.64 Hf, 12.71 Th, 1.53 U, and 13.35 Y (all data in microg/g). Paddy soils were classified into groups based on morphology and climate. Higher contents of Th and U were found in the wet zone lowland soils whereas the higher Ti contents were observed in dry zone soils. Arsenic, Zr and Hf contents were comparatively similar in all regions. Factor analysis was used to identify the relationships between the contents of elements.