C E H AUSES AND FFECTS OF EAVY METAL POLLUTION No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or by any means. The publisher has taken reasonable care in the preparation of this digital document, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained herein. This digital document is sold with the clear understanding that the publisher is not engaged in rendering legal, medical or any other professional services. C E H AUSES AND FFECTS OF EAVY METAL POLLUTION MIKEL L. SÁNCHEZ EDITOR Nova Science Publishers, Inc. New York Copyright © 2008 by Nova Science Publishers, Inc. All rights reserved. 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LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA Causes and effects of heavy metal pollution / Mikel L. Sánchez (editor). p. cm. Includes bibliographical references and index. ISBN 978-1-60876-255-2 (E-Book) 1. Heavy metals--Environmental aspects. I. Sánchez, Mikel L. TD196.M4C38 2008 628.5'2--dc22 2008030631 Published by Nova Science Publishers, Inc. (cid:30) New York CONTENTS Preface vii Chapter 1 Impacts of the Mining and Smelting Activities to the Environment – Slovenian Case Studies 1 Gorazd Žibret and Robert Šajn Chapter 2 Treatment of Acid Mine Drainage by a Combined Chemical/Biological Column Apparatus: Mechanisms of Heavy Metal Removal 81 Francesca Pagnanelli, Ida De Michelis, Michele Di Tommaso, Francesco Ferella, LuigiToro and Francesco Vegliò Chapter 3 Assisted Phytoextraction for Abandoned Mining Areas Remediation 107 Alessia Cao, Alessandra Carucci and Tiziana Lai Chapter 4 Phytochelatins in Wild Plants from Guanajuato City – an Important Silver and Gold Mining Center in Mexico 123 Kazimierz Wrobel, Julio Alberto Landero Figueroa and Katarzyna Wrobel Chapter 5 Fate of Trace Elements in the Venice Lagoon Watershed and Conterminous Areas (Italy) 137 C. Bini Chapter 6 Anthropogenic Mercury Pollution in Aquatic Systems: A Review of Enviromental Fate and Human Health Risks 173 S. Michele Harmon Chapter 7 In Situ Measurement of Metal Concentration in River Water Using Portable Edxrf System 201 Fábio L. Melquiades, Carlos R. Appoloni, Paulo S. Parreira and Wislley D. Silva Chapter 8 Biomonitoring of Heavy Metal Pollution in the Marine Environment Using Indicator Organisms 249 Joseph Selvin, S. Shanmugha Priya, G. Seghal Kiran and Saroj Bhosle vi Contents Chapter 9 Heavy Metal Contamination in Selected Urban Coastal Regions in US and China 265 Huan Feng, Weiguo Zhang, Luoping Zhang, Xu-Chen Wang, Lizhong Yu and Danlin Yu Chapter 10 Monitoring Heavy Metal Pollution with Transgenic Plants 287 Igor Kovalchuk and Olga Kovalchuk Chapter 11 Geochemistry of Major and Trace Elements in Core Sediments of Sunderban Delta, India: An Assessment of Metal Pollution Using Atomic Absorption Spectrometer and Inductively Coupled Plasma Mass Spectrometry 305 A. Bhattacharya, K.K. Satpathy, M.V.R. Prasad, J. Canario, M. Chatterjee, S.K Sarkar, V. Branco, B. Bhattacharya, A. K. Bandyopadhyay and Md. Aftab Alam Chapter 12 Heavy Metal Pollution, Risk Assessment and Remediation in Paddy Soil Environment: Research Experiences and Perspectives in Korea 341 Jae E. Yang, Yong Sik Ok, Won-Il Kim and Jin-Soo Lee Index 371 PREFACE A heavy metal is a member of an ill-defined subset of elements that exhibit metallic properties, which would mainly include the transition metals, some metalloids, lanthanides, and actinides. Many different definitions have been proposed—some based on density, some on atomic number or atomic weight, and some on chemical properties or toxicity. The term heavy metal has been called "meaningless and misleading" in a IUPAC technical report due to the contradictory definitions and its lack of a "coherent scientific basis". As discussed below, depending on context, heavy metal can include elements lighter than carbon and can exclude some of the heaviest metals. One source defines "heavy metal" as "... common transition metals, such as copper, lead, and zinc. These metals are a cause of environmental pollution (heavy-metal pollution) from a number of sources, including lead in petrol, industrial effluents, and leaching of metal ions from the soil into lakes and rivers by acid rain. Chapter 1 - Slovenia, a central European state with an area of little more than 20.000 km2, has a more than 500-year of metal mining and smelting tradition. In the previous century, almost all mines and smelting plants were closed, but numerous anomalies were left behind with total area of approximately 70-80 km2, where the concentrations of the heavy metals in soils exceed the critical values, concerning Slovenian legislation. The structure of this paper is as follows: introduction contains the brief description of the historical background of mining and smelting tradition in Slovenia and a description of each site of detailed research from historical perspective. After materials and methods chapter which contains the description of sampling, samples preparation, and data processing, the regional geochemical trends, based on the 60 sampling points in the Slovenian unpolluted areas, is presented together with comparison with urban areas. Further on the detailed description of the geochemical anomalies in the most polluted areas due to metal mining, smelting and iron working follow. The methodology has been the soil and attic dust sampling around past and present smelting plants. The areas, where the pollution has been researched in details, are: • Mežica valley: Pb and Zn mine with smeltery and ironworks where mining tradition exists since 1665 with the consequence of heavy Pb and Zn pollution, 114 sampling points where soil and attic dust has been sampled; covered area – 101 km2; • Celje: 100 years of Zn smelting tradition and 150 years of ironworks left behind heavy Zn and Cd pollution, 99 sampling points where soil and attic dust has been collected, covered area - 92 km2; viii Mikel L. Sánchez • Jesenice: iron working activities (Jesenice Ironworks company exists from 1937, but small scale smelting is dated back to the middle ages) left behind moderate Cd, Pb, Hg and Zn pollution, 44 sampling locations of soil profiles, covered area – 113 km2; • Litija: polymetallic (Pb, Zn, Hg, Ag, Ba) mining with smaller scale smelting activities, dating back to the roman times; moderate As, Mo, Hg, Pb, Sb and Sn pollution, 38 sampling points where soil and attic dust has been collected; covered area – approx. 30 km2. • Idrija: world's second largest Hg mine with smelting plant where 500 years of Hg production left heavy Hg pollution, 103 sampling points where soil and attic dust has been collected; covered area – 160 km2. A geochemical characteristic of each area is presented with non-parametrical statistical properties (median and average value, range, P25-P75). Bivariate statistics include correlation coefficients between sampling media and multivariate statistics (factor analysis) presents geochemical associations. Scale of the pollution on each area is presented with the help of enrichment factors, calculated on the basis of slovenian background values. Further on maps of spatial distribution of factor scores and of selected chemical elements are made. Discussion contains the brief summary of the research and the short descriptions of most evident anomalies. Chapter 2 - Natural oxidation of sulphide minerals, exposed to the combined action of oxygen and water, results in the worst environmental problem associated with mining activities, i.e. acid mine drainage (AMD). Waters polluted by AMD are often characterised by low pH, elevated concentrations of iron, sulphates and toxic metals. Biological remediation options in passive systems (permeable reactive barriers, PRB) usually exploit sulphur production by sulphate reducing bacteria, SRB. In this report a combined chemical-biological treatment was tested for decontamination of synthetic AMD containing iron, arsenic, copper, manganese and zinc. Particular attention was paid to the investigation of the mechanisms involved in pollutant removal (chemical precipitation, sorption, bioprecipitation and biosorption) as a fundamental preliminary step for permeable reactive barrier design and long term performance estimation. Experimental tests were performed both in batch reactors and in a two-column apparatus for sequential treatment by chemical precipitation (first column filled with natural limestone) followed by bioprecipitation/biosorption (second column filled with a natural organic mixture inoculated by sulphate reducing bacteria). Distinct mechanisms of removal for each metal were identified by combining theoretical data of metal solution chemistry, and results obtained from independent experimental tests: batch and column tests, blank tests using natural organic mixture as biosorbing materials, acid digestions, and selective extractions of metals using solid samples of filling material after column dismantlement. This analysis allowed isolating metal-specific mechanism of abatement and denoted the relevant contribution of biosorption phenomena in metal removal in biological column. This contribution, generally neglected in biological PRB design with respect to bioprecipitation, should be taken into account in order to avoid misleading estimation of SRB performance and also to better estimate PRB duration. Preface ix Chapter 3 - The remediation of mining areas represents a relevant environmental problem in all Europe. The high concentration of heavy metals and the lack of nutrients determines the desertification of wide areas. In Sardinia (Italy) the poor management of Montevecchio – Ingurtosu mining district after mine closure caused the dispersion of high amounts of contaminants by wind and water erosion on wide areas. The wide extension of the contaminated area and the high level of contamination by heavy metals make the application of phytoextraction feasible for this area. The environmental risk related to the presence of heavy metals can be evaluated by determining the bioavailable metal fraction in soil. The Department of Geoengineering and Environmental Technologies of the University of Cagliari made experiments of phytoextraction and assisted phytoextraction both with plants having a high biomass production (Mirabilis jalapa) and with native species (Cistus salvifoliius, Scrophularia canina and Teucrium flavum). Easily biodegradable chelating agents were applied in laboratory experiences (MGDA - methylglycine diacetic acid, S,S-EDDS - [S, S]- ethylenediaminedisuccinic acid, IDSA - iminodisuccinic acid). The ability of the plant species to tolerate and accumulate heavy metals demonstrated the applicability of phytoextraction to the abandoned mining areas remediation. Chapter 4 - Phytochelatins (PCs) are a group of small, metal-binding peptides that are biosynthesized by higher plants, some fungi and algae in the response to heavy metal exposure. One actual research topic focuses on better understanding the global effect that all elements present in natural environments exert on the PCs production by plants. In this work, PCs levels were evaluated in the wild plants, chronically exposed to low or moderate levels of heavy metals. The quantification of total PCs in plant extracts was carried out by HPLC with fluorimetric detection, after derivatization of free –SH groups with monobromobimane. Additionally, the distribution of metals in molecular mass (MM) fractions of these same extracts was studied by size exclusion chromatography with on-line UV and ICP-MS detection. All samples were collected in Guanajuato city (Mexico), which has long been an important silver and gold mining area. Among different metals reported in Guanajuato soils, lead, cadmium, copper and silver were selected in this study, because of their capability to induce phytochelatins in plants. The common plants from this region were analyzed, namely: Ricinus communis (castor bean), Tithonia diversifolia (Mexican sunflower) and Opuntia ficus (nopal). The analytical approach involved the ICP-MS analysis of total elements in soil, soil fractions and wild plants and also the evaluation of relationships between PCs, metal levels found in plants/soil and different soil parameters. In the analysis of plants, PC-2, PC-3 and PC-4 were detected in nopal, PC-2 in castor bean, while in Mexican flower no phytochelatins were found. In further development, the extracts of soil humic substances were obtained and the distribution of metals in molecular mass (MM) fractions was studied by size exclusion chromatography with on-line UV and ICP-MS detection. The soil humic substances (HS) were also assessed. In search of possible relationship between the parameters measured, the statistical analysis of correlation was performed. The results obtained indicate that the binding of metals to soil HS contributes in lowering their uptake by castor bean plant. On the other hand, the soils collected at nopal roots presented low HS levels and no correlation with metals in plant was found. The results obtained in the sequential extraction of soils and the abundance of sulfide minerals in Guanajuato indicate that the sulfide bound metals were the primary forms of Pb, Cu and Cd in soil adjacent to nopal roots. Owing to their generally poor solubility, rizosphere processes should be important in mobilizing metals and their uptake by nopal.
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