Table Of ContentSoil 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
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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
