Soil Biology Irena Sherameti Ajit Varma Editors Heavy Metal Contamination of Soils Monitoring and Remediation Soil Biology Volume 44 Series Editor AjitVarma,AmityInstituteofMicrobialTechnology, Amity University Uttar Pradesh, Noida, UP, India More information about this series at http://www.springer.com/series/5138 Irena Sherameti (cid:129) Ajit Varma Editors Heavy Metal Contamination of Soils Monitoring and Remediation Editors IrenaSherameti AjitVarma Institutfu¨rAllgemeineBotanikund AmityInstituteofMicrobialTechnology Pflanzenphysiologie AmityUniversityUttarPradesh Universita¨tJena Noida Jena UttarPradesh Germany India ISSN1613-3382 ISSN2196-4831 (electronic) SoilBiology ISBN978-3-319-14525-9 ISBN978-3-319-14526-6 (eBook) DOI10.1007/978-3-319-14526-6 LibraryofCongressControlNumber:2015937019 SpringerChamHeidelbergNewYorkDordrechtLondon ©SpringerInternationalPublishingSwitzerland2015 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilarmethodologynowknownorhereafterdeveloped. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. Thepublisher,theauthorsandtheeditorsaresafetoassumethattheadviceandinformationinthis book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained hereinorforanyerrorsoromissionsthatmayhavebeenmade. Printedonacid-freepaper Springer International Publishing AG Switzerland is part of Springer Science+Business Media (www.springer.com) Foreword When the esteemed editors, Irena Sherameti and Ajit Varma, asked me to contri- bute the foreword for this book, I felt very honored and agreed spontaneously. The initial elation gave way very soon a certain disillusionment. Even temporary panicaroseafterafirstlookonthelistwiththecompetentauthorship,thesubject being “heavy metals and soil” from the perspective of a researcher who for the lastseveralyearswasmainlyconcernedwithmicrobiallifeinmustandwine. What gradually calmed me is the idea that all the knowledge of our time is availableontheInternet,whichcanbeeasilyabsorbed,mixed,andpresentedasour own new insights. After some reflection, however, I became aware that at least metals,thedefinitionof“heavymetal”isnotaseasyasitsounds,havemetmehere and there over the course of my scientific career. Therefore, I decided to forego “DikipediaandWoogle,”resortingasfaraspossibletoownexperiences. Isthereanyrelationbetweenheavymetalsandwinemaking?Yes! The metal content in wines originates from primary and secondary sources. The primary source is, in this case, the natural content, which comes from the vineyard soil going up through the vine roots into the grape, and finally into the wine.Thesecondarysourcesareimpuritiesofgeogenicandanthropogenicorigins. These include fertilizers, pesticides, grape harvest, wine treatment, and wine storage. For example, chemical formulations of copper and zinc are included in fungicides.Informertimes,problemsdevelopedfrominputsofironbyrustynails in wood barrels and lead by motorcar traffic near vineyards. Nowadays, higher amounts of aluminum may enter the wine via metal tanks without internal lining andmorepreviouslybywinebottlesandcaps. Inmaturegrapes,thefollowingaverageelementalconcentrations(mgl(cid:1)1)were measuredbyourcolleaguesattheInstituteofNuclearChemistryoftheUniversity ofMainz:potassium(1,600),calcium(80),magnesium(60),sodium(4.0),manga- nese(0.9),aluminum(0.6),copper(0.5),zinc(0.4),andrubidium(0.3). InberryripeningandthealcoholfermentationbythewineyeastSaccharomyces cerevisiae, these metals play an important role, especially zinc as a cofactor or structural component in nearly 300 proteins. It is a constituent of the alcohol v vi Foreword dehydrogenaseandadeficiencycanleadtostuckgrapemustfermentation.Forthe malolactic fermentation (also called secondary fermentation), namely the conver- sion of malate to lactate through the wine bacterium Oenococcus oeni, another metal is necessary: manganese as part of the malolactic enzyme and as a growth factor. Copper(Cu)istheonly“real”heavymetal,whichisregularlydetectableinmust and wine. It may serve as an example for the ambivalent properties and the problemsrelatedwith the use ofheavy metalsilluminated inthisbook. Copper is an essential trace element in living systems, where it serves as a cofactor in enzymes that function in energy generation, oxygen transport, detoxification, melanization, blood clotting, signal transduction, and many other processes. The physiologicaloxidationstatesofcopperareCu1+andCu2+,whereasCu3+isnota biologicallyrelevantspeciesbecauseofthehighredoxpotentialoftheCu3+/Cu2+ couple. The copper in the active sites of redox proteins (e.g., tyrosinase, laccase, cytochrome-c-oxidase, superoxide dismutase) has been assigned to three main classes. Our peers at the Institute for Molecular Biophysics of the University of Mainz foundthatcopperinthebluebloodofinsects(hemocyanins)couldmediateoxygen transportaswellasinducetyrosinaseactivity.Theevolutionoftheaerobicorganic world might not be the same without the oxygen activation by inorganic copper. Similarly, iron is involved in various redox reactions: as cofactor of enzymes (in Fe-S clusters) and in the hemoglobin. Furthermore, according to established theories of Wa¨chtersha¨user and others, the origin of life was driven by catalytic activitiesatthesurfaceofiron-sulfurminerals(pyrite). TheWorldHealthOrganization(WHO)hascalculatedadailydemandofabout 0.08mgCukg(cid:1)1bodyweightforinfantsandchildrenandof0.03mgCukg(cid:1)1body weightforadults. For drinking water, the guidelines of the WHO recommend an upper concen- tration of 2.0 mg l(cid:1)1; in the United States, the permissible limit is 1.0 mg l(cid:1)1. Agriculturehasbecomeoneofthemostimportantfieldsofcoppercontaminationin soilandplantmaterial,whereitisusedasoneoftheearliestfungicides.Thefalse mildew, a plant disease caused by the fungus Plasmopara viticola, could be successfully inhibited with the so-called Bordeaux mixture, consisting of burnt lime(CaO)andacoppersulfatesolution.Soilsofwine-growingareas,whichhave been treated over several decades with these compounds, are enriched with high copperconcentrations,which sometimes exceed considerably thepermittedlimits oftheEuropeancommunityregulations(140mgkg(cid:1)1). Thus,itisnotsurprisingthatcopperisamongthemostabundantheavymetalsin wine, originatingfrom the soil, plant protectionproducts, and winemaking equip- ment. Moreover, addition of copper sulfate (up to 10 mg l(cid:1)1) is a common oenological practice to remove sulfurous off-flavor compounds by precipitation and subsequent filtration. In a recent study, the copper content determined in 72 wines averaged 0.18 mg l(cid:1)1 with a maximum of 0.55 mg l(cid:1)1. The copper concentration limit recommended by the Organization International de la Vigne Foreword vii et du Vin (OIV) in wines is equal to 1.0 mg l(cid:1)1. National regulations allow the presenceof2.0mgCul(cid:1)1inGermanwinesanddrinkingwater. ElevatedCuconcentrations,especiallyincombinationwithotherheavymetals found inwine,e.g.,iron,manganese, zinc, nickel, lead, andvanadium, bear some unaccountablehealthrisksfortheconsumers.Astypicalforheavymetals,copper inhibits enzyme activities when present at higher concentrations. Wine-relevant microorganismsshowastrain-dependentgrowthinhibitionatdifferentCuconcen- trations, e.g., Oenococcus oeni (5–10 mg l(cid:1)1), Saccharomyces cerevisiae (32–75 mg l(cid:1)1), Lactobacillus fermentum (75–300 mg l(cid:1)1), or Lactobacillus mesenteroides (55–150 mg l(cid:1)1). High amounts (>20 mg l(cid:1)1) can even have an impactongrapemustfermentations. Furthermore,Cuconcentrations>0.5mgl(cid:1)1exertvariousundesirableeffectsin winelikeametallictasteandhazeformation.Thebrowningofwine,primarilydue totheenzymaticandchemicaloxidationofthephenoliccompounds,representsone of the most feared processes, which may arise during winemaking. Wine grapes possess a very high phenolic content compared to many other fruits and crops. Thephenoliccompoundssignificantlyaffectthecolor,odor,andtasteofthewine. Inadditiontothevisualandgustatoryproperties,theyserveasfreeradicalscaven- gers and have antioxidant effects. Some polyphenols have been associated with anticarcinogenic, anti-inflammatory, antibacterial, and antihepatotoxic properties. Therefore, they have a high impact on the nutrient quality of wine. The catalytic effectofinorganiccopperandutmostthereleaseoflaccase,amulticopperenzyme, into must from grapes infected with the phytopathogenic fungus Botrytis cinerea causeasignificantreductionofthecontentofbeneficialphenoliccompounds. Ifthecoppercontentinwineexceedsthepermissiblelimits,proceduresmustbe applied for metal removal. A frequently used method is the “blue fining” with potassium hexacyanoferrate (II) which forms an insoluble complex with copper ions. The remaining cyanides react with the existing iron to insoluble compounds and precipitate. In case of an iron deficiency, an excess of highly toxic cyanides remainsinthewine,makingitcommerciallyunsalable.Inaddition,thetoxicwaste raises environmental problems. Although the use of bentonites and artificial ion-exchange resins has been demonstrated to be effective in reducing the metal contents in wines, these procedures may cause off-taste and color loss of the product. Alternativemethodsofmetalremovalusebiomass(bacteria,yeasts,fungi,and algae) as sorbents. A relatively slow active process by which metal ions are transported inside the cells characterizes the bioaccumulation. Biosorption is defined as a passive, nonmetabolic process involving complexation, chelation, ion-exchange, adsorption, and microprecipitation. Bacterial and yeast cells are such able to accumulate, in either active or passive ways, a large variety of toxic heavymetalslikecadmium,lead,andeventheradionuclideuranium.Recentlywe founddifferentstrainsoflactobacilliusefultoremovecopperfromwinesamples. Thenegativelychargedproteinaceouscell-wallenvelope(S-layer)oftheseGram- positivebacteriaservesastheinitialbindingmatrix. viii Foreword Thesetoolsareusefulforaquaticsystems,butforsoilenvironments,improved phytoremediationstrategies have to be developed. All the more so because heavy metals byno means existinert innature, butcomevia the foodchain,conjugated with organic molecules. In this manner, new element species can arise with dramatically increased toxicity. Members of our working group, for example, could demonstrate the formation of high toxic methyl mercury from inorganic mercury by intestinal bacteria in the gut of earthworms. Furthermore, increasing anthropogenic production of metallic nanoparticles leads to compounds with new properties.Analmostuncontrolledapplicationanddisseminationofmetallicmate- rials, for example, titanium oxide in sunscreens, already leads to unpredictable consequencesforhumanhealthandenvironment.Theresponsibleuseandcareful scientific monitoring in the development of such novel metallic materials is the need of the hour. Only in this way we can profit from their beneficial properties withoutharmingnatureandourselves. Mainz,Germany HaraldClaus InstituteofMicrobiologyandWineResearch, JohannesGutenberg-UniversityMainz Preface HeavymetalsoccurnaturallyasconstituentsoftheEarth’scrust(Singhetal.2011) and are introduced to ecosystems via natural processes (Mahmood et al. 2012). Since they are nonbiodegradable, they can accumulate in the environment (Alietal.2013)andcausecontamination. Nowadays,contaminationofsoilswith heavymetalshasbecomeaworldwideproblemandaseriousthreattotheenviron- mentbecauseofincreasinganthropogenicactivitieslikemining,usesoffertilizers, wastes,sewagesludge,pesticides,wastewaterirrigation,coalcombustionresidues, atmospheric deposition, etc. (Wuana and Okieimen 2011). In a critical review, Su et al. (2014) conclude that heavy metal contamination refers to the excessive depositionoftoxicheavymetalsinthesoilcausedbyhumanactivities. Thisnewvolumewillfocusontheachievementsofthelastyearsonsourcesof heavy metals in soils and monitoring strategies, adaption strategies of plants and bacteria in response to heavy metals, approaches for the remediation of contami- nated soils, and genetic engineering as a tool to cleaning up contaminated soils. Thevolumeisorganizedin5partsandcontains23chapters. Part I: Sources of Heavy Metals in Soils Chapters 1–4 will deliver general information on heavy metals in the post-catastrophic and agricultural soils, contamination and its impact on soil bio- logicalqualityinurbanagriculture,multiple-phaseevaluationofcoppergeochem- istry,sourcesofheavymetals,andfactorsinfluencingtheircontentsinsoils. Chapter1,byVesnaStankovJovanovic´,VioletaMitic´,SnezˇanaNikolic´Mandic´, Marija Ilic´, and Strahinja Simonovic´, focuses on heavy metals in the post- catastrophic soils and discusses the distribution pattern of heavy metals in soils aftercatastrophiceventsandextremephenomena,whichcanbeinducedbyhuman activities or natural disasters. The authors conclude that metals can be easily transferredfromoneareatoanotherbywaterandair.Thistransferismoredynamic ix
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