Jaume Bech

Arsenic and heavy metal contamination of soil and vegetation around a copper mine in Northern Peru

Abstract At present, very little information is available on either the environmental impact or the biogeochemistry of mine sites in Latin America. Here we present preliminary results on contamination of soils and plants around a copper mine in the Andes of Northern Peru. Plants and soils were sampled at six sites ranging from low (S1) to high phytotoxicity (S6); samples were analysed for concentrations of As and heavy metals. Stepwise multiple regression analysis was used in order to determine the soil factors that significantly influenced As and metal availability. High As and Cu concentrations in soil extracts (ammonium acetate-EDTA), in addition to low pH and high Al availability, seem to be the most important soil factors that limit plant performance around the mice. A high organic matter content favoured Cu and Al extractability. Nevertheless, phytotoxicity was more intense at sites with low organic matter concentrations. Unusually high concentrations of As and metal concentrations were detected in leaves of some species (e.g. in Bidens cynapiifolia up to 1430 μg/g dry wt. As, 437 Zn, 620 Cu, 6510 Al and 5.7% Fe) while others (e.g. Eriochloa ramosa) more effectively restricted metal transport to the shoots. These plant species seem interesting for future investigations on both metal tolerance mechanisms and revegetation of contaminated soils at the numerous mine sites located at high altitudes in equatorial regions.

Copper in plant species in a copper gradient in Catalonia (North East Spain) and their potential for phytoremediation

The accumulation of Cu in roots and shoots of 32 plant species growing on soils with a wide range of Cu concentrations (30–18 500 μg g−1 total soil Cu) located in Collserola Mountain (Barcelona, Spain) was analysed. High Cu availability decreased the species diversity in the Hyparrhenietum hirto-pubescentis, the natural plant association at the study sites. Shoot and root Cu concentrations in relation to extractable soil Cu concentrations were used for the evaluation of the Cu resistance strategy in the different species. Saturation of Cu accumulation in roots was observed in most species. Hyparrhenia hirta was the most efficient shoot excluder, while the linear increase of shoot Cu with the Cu soil concentration exhibited the highest slope in Hirschfeldia incana. Most species accumulated more Cu in roots than in shoots. High shoot/root Cu ratios were only found in the highly Cu-resistant Hirschfeldia incana, in the resistant or moderately resistant Spartium junceum and Reseda sp. (R. lutea and R. phyteuma), and in the much less resistant Ononis natrix. Only two species, Hirschfeldia incana and Sedum sediforme were able to support the extreme Cu-toxicity conditions on soils with 5000–16 800 μg g−1 extractable Cu. Among the grass species tested Hyparrhenia hirta was the most Cu-resistant species (up to 1950 μg g−1 extractable soil Cu). The potential usefulness of these pseudometallophytes for phytoremediation of Cu-contaminated soils is discussed.

Establishment of the background levels of some trace elements in soils of NE Spain with probability plots

Abstract The total content of Ba, Cr, Cu, Ni, Pb, V and Zn, determined by means of X-ray fluorescence was studied in soils of an agro-industrial area near Barcelona (NE Spain) in order to establish their background levels. A total of 363 samples were analysed, of which 268 belonged to 67 slightly disturbed and representative soil profiles. The remainder were taken at the soil surface (0–5 cm) in a polluted area located near a composting plant. The background ranges were established with probability plots and the upper limits of the resulting ranges were compared with those reported in the literature. In order to study the statistical distribution of the trace elements in the soils of the area, the Kolmogorov-Smirnov test of distribution fitting was applied. The upper limits of the established background ranges were: Ba, 1762 mg/kg; Cr, 275 mg/kg; Cu, 145 mg/kg; Ni, 83 mg/kg; Pb, 91 mg/kg; V, 183 mg/kg; and Zn, 326 mg/kg. It was concluded that probability plots seemed to be a reliable statistical method for establishing the background contents of these elements in the soils of the area studied. The trace elements investigated were distributed in these soils following the log-normal law.

The iron content of some red Mediterranean soils from northeast Spain and its pedogenic significance

Abstract Alfisols cover 18% of the surface of the NE edge of the Garraf massif (SE of Barcelona, Catalonia). Most of these are Mediterranean red soils. Some representative pedons, especially over Mesozoic limestones, are discussed in this paper. Climate of the zone is littoral Mediterranean (mean temperature 16°C, precipitation 650 mm). Pedoclimatic regimes are xeric and thermic. Vegetation is Quercetum ilicis galloprovinciale. Horizon B is 5YR and 2.5YR in Munsell Hue with a pHw of 7.2 to 8.6. All of them are base saturated and the majority recarbonated. Organic matter content is 2.5%. Some have an “isohumic” character. The illuviation clay index ranges from 0.37 to 0.87 and the mean value of the illuviation Fe index is 0.76. The nearly constant Fed/clay ratio indicates co-illuviation. Values for Fed are between 0.40% and 2.81%. The mean Feo is 0.057%, and it ranges between 0 to 0.14%. Generally redness rating (RR) increases with Fed. Values of Fed/Fe1 vary from 0.22 to 0.82 and the mean is 0.54. Rubefaction according to redness rating is moderate. Taxonomically, Calcic Haploxeralfs predominate and are located at 50–70 m above sea level. Calcic Palexeralfs (at 70–80 m and again at 150 m) and Petrocalcic Palexeralfs (at 80–130 m) are also found. Typic Haploxeralfs are frequent over limestones at higher altitudes (260 m) or overlying silicic rocks found at 35 65 m. According to the 1967 French Classification System they are Red fersialitic and Brown fersialitic soils and some are integrades with Cinnamotnic soils (“marron encroute”).

PHEs, Environment and Human Health

The atmosphere represents a complex system influenced by the chemical and physical processes that occur at the Earth surface. These processes include emissions, transport, lifetimes and fates of several anthropogenic and biogenic/ geogenic chemicals emitted from a wide variety of sources. Among these chemicals, some are considered air pollutants, i.e. any substance present in ambient air and likely to have harmful effects on human health and/or the environment as a whole. Metals, and in general elements, are natural components of the earth’s crust and constituents of all ecosystems. In the atmosphere, they are mainly related to particle phase but also they can be present in a liquid phase due to the dissolution of aerosol particles in the water drops. Whatever their origin, both natural and anthropogenic, most elements, and in particular heavy metals, are dangerous because they tend to bio-accumulate in the human body. This chapter describes a general overview on elements and their sources and potential effects on human health in atmosphere. Furthermore, considering the increase of the interest on biological fraction of PM, a briefly description of bioaerosols will be made. Recently, the number of evidence that describes how this fraction may play a key role in the effects of PM on biological systems with negative impacts on human health and ecosystem functioning are increased. Mathematical model applied to air pollution studies will be briefly described. Mathematical models (dispersion and transport model), that predict the concentration and the dispersion of primary and secondary pollutants in atmosphere, represent a fundamental tool in the atmospheric studies to develop health and/or environmental risk assessment and various control strategy actions. Moreover, some specific elements (Sb, Tl, V and Be) will be discussed investigating the effects on health, main sources application and reviewing the most recent studies. G. Rampazzo (*) • E. Innocente • E. Pecorari • S. Squizzato • G. Valotto Dipartimento di Scienze Ambientali, Informatica e Statistica, Universià Ca’ Foscari Venezia, Calle Larga S. Marta, Dorsoduro 2137, 30123 Venezia, Italy e-mail: rampazzo@unive.it C. Bini and J. Bech (eds.), PHEs, Environment and Human Health, DOI 10.1007/978-94-017-8965-3_1,

Cesium-137 contamination of oak (Quercus petrae Liebl.) from sub-mediterranean zone in South Bulgaria.

This study focuses on the cesium-137 ((137)Cs) contamination in grass and in different compartments of oak trees growing in ecosystems, located in the zone with sub-mediterranean climate in South Bulgaria, characterized with high summer temperatures, low precipitation and often periods of drought. In 2008, three experimental sites - PP1, PP2, PP3 - were sampled in oak ecosystems from Maleshevska Mountain at 900 m above sea level. Samples from grass species and oak tree leaves, branches with different diameter, wood disks and bark were analyzed for (137)Cs activity with gamma-spectrometry. The soil-to-plant transfer factor (TF) values for (137)Cs were estimated differentiating different tree compartments. Our findings showed relatively high activity concentrations of (137)Cs in oak trees even 22 years after the Chernobyl accident. The grass under oak was less contaminated compared with the oak trees. The different organs of oak trees could be distinguished according to the (137)Cs contamination as follows: bark>branches (d<1 cm)>leaves>branches (d>3 cm)>wood. The relatively higher contamination of bark compared with the new-formed biomass suggested that a significant part of (137)Cs was accumulated as a result of direct adsorption at the time of the main contamination event. The TF values obtained and the presence of (137)Cs in the branches, leaves and in the wood formed after 1986 confirmed that 22 years after the contamination, the main mechanism of (137)Cs entrance in tree biomass was the root uptake.

Assessment of the Heavy Metal Pollution Effects on the Soil Respiration in the Baix Llobregat (Catalonia, NE Spain)

A main goal of investigations is to determine could a soilrespiration be an indicator of the soil pollution. In this case a measured levelof the soil oxygen consumption depends of its pollution. It alsomeans that the pollution reduces biological processes in edaphon.Investigated soil samples were taken from polluted andnon-polluted places in the Baix Llobregat near Barcelona (Catalonia, NE Spain). Soil samples were taken from the top ofsoil (0–5 cm) without a litter. Soil analysis were done, determining percentage shares of coarsefragments, coarse sand, fine sand, coarse silt, fine silt, clay,CaCO3, organic matter as well as water pH and conductivityCE (1:5 [mS cm-1]). Also were determined (in mg kg-1)quantities of heavy metals, as Fe, Al, Mn, Zn, Cr, Ni, V, Cu, Cd, Pb.The soil respiration was investigated in temperatures15 and 30 °C and with controlled humidity.The respiration in 30 °C is number of times greater thenin 15 °C both for polluted and non-polluted soils.Particularly high coefficients of correlation between the soilrespiration and soil pollution in polluted soils were obtainedfor Pb: r = 0.75 in 15 °C and r = 0.98 in30 °C; for Ba: 0.90 and 0.57; for V: 0.99 and 0.81. In non-polluted soils highest correlation coefficients are for Pb: r = 0.70 in 15 °C; Fe: 0.60 and 0.72; Al: 0.68 and0.64; Mn: 0.51 and 0.66; Ba: 0.63 and 0.61; Cr: 0.94 and0.70; Ni: 0.64 and 0.65; Cu: 0.69 and 0.48; as well as V: 0.62in 15 °C; and Cd: 0.69 in 15 °C.This way the soil respiration could be a good indicator of the soil pollution.

Geochemical characterisation of surface waters, topsoils and efflorescences in a historic metal-mining area in Spain

PurposeMining activities generate large amounts of wastes that may contain potentially toxic elements (PTE), which, if released into the environment, may cause air, water and soil pollution long after mining operations have ceased. This paper describes the environmental relevance of efflorescences, topsoils and surface waters from the abandoned mine of Sierra Minera of Cartagena-La Unión, SE Spain. The exposure of the population to arsenic and the associated risk were also assessed.Materials and methodsA total of 10 topsoils and surface waters and 11 efflorescences affected at varying degrees by mining activities were studied. The total potentially toxic element content (As, Cd, Cu, Fe, Pb and Zn) was determined in all samples. In addition, the mineralogical composition of solid samples was determined by X-ray diffraction and some efflorescences were also analysed using a scanning electron microscopy-energy dispersive X-ray spectrometer. Finally, an arsenic-intake risk assessment was carried out, both as regards carcinogenic and non-carcinogenic effects and considering the total and the bioaccesible As content.Results and discussionThe study area is heavily polluted as a result of historical mining and processing activities, during which time great amounts of wastes were produced, characterised by a high PTE content, acidic pH and minerals resulting from supergene alteration. The supergene mineralogical assemblages include soluble metal salts, mainly sulphates, iron hydroxysulphates and iron oxyhydroxides, all of which form ochreous precipitates. Topsoil samples showed risk values and hazard quotients higher than the reference levels, particularly for children. In the efflorescences, these values were lower but still unacceptable.ConclusionsThe efflorescences are of significance for monitoring purposes because they are involved in cycles of retention release of hydrogen ions, sulphate and potentially toxic elements. In addition, in a semi-arid climate, such as the study area, these minerals contribute to our understanding of the response of the system to episodic rainfall events. In general, it was observed that the arsenic in collected samples represent a potential risk for human health through ingestion.

Baseline Concentrations of Potentially Toxic Elements in Natural Surface Soils in Torrelles (Spain)

The objective of this article is to establish baseline concentrations of Ba, Cr, Cu, Ni, Pb, Sr, V, and Zn (aqua regia-extractable) in natural surface soils of the Torrelles Municipal District and to investigate the relationships between these elements and soil properties and between the element concentrations themselves. Upper baseline concentrations of these elements were (mg kg −1): Ba 272.6, Cr 40.8, Cu 31.0, Ni 29.9, Pb 68.1, Sr 83.0, V 49.7, and Zn 132.7; most corresponded with the values reported in the literature. Correlation analysis showed that total Fe and Al have the strongest relationships with trace elements.

Remediation of Potentially Toxic Elements in Contaminated Soils

This chapter aims to offer an overview of the main remediation methods of potentially toxic elements in contaminated soils, mainly heavy metals, metalloids and radionuclides, focusing on their essential characteristics, advantages and limitations. It consists of two main groups of technologies: the first group dealing with containment and confinement, minimizing their toxicity, mobility and bioavailability. Containment measures include covering, sealing, encapsulation and immobilization through solidification (cement-based, polyethylene and resine binders, bituminization or asphalt batching and vitrification or glassification) and stabilization with inorganic and organic amendments. The second group, remediation with decontamination is based on the remotion, clean up and/or destruction of contaminants. This group includes mechanical procedures (excavation, transport and disposal to landfills), physical separations, chemical technologies such as soil washing with leaching or precipitation of potentially toxic elements, soil flushing, thermal treatments (desorption, pyrometallurgical processes and incineration) and electrokinetic technologies (electromigration, electroosmosis, electrophoresis and combinations of electrokinetics with other techniques). There are also two approaches of biological nature: bioremediation (biosorption, bioreduction, biomineralization and bioleaching-with some examples from Korea) and phytoremediation (phytoextraction, including chelate-assisted phytoextraction, phytostabilization, phytoremediation in mining activities -with examples from Portugal, Spain, Ecuador, Peru and Chile mainly-, phytovolatilisation and phytomining).