Seminar Report On

FATE, TRANSPORT AND ENVIRONMENTAL EFFECTS OF NANOPARTICLES RELEASED IN THE ENVIRONMENT

Submitted by
Smarika Kulshrestha

(Roll Number: 133180002)

Under the supervision of

Supervisor: Prof. XYZ

Centre for Environmental Science and En ineerin !N"!#N !NS$!$%$E &' $EC(N&)&*Y+ ,&-,#Y
October 31 2013

#PPR&.#) S(EE$
This seminar report entitled "Fate, Transport and Environmental Effects of Nanoparticles Released in the Environment" prepared by Smarika Kulshrestha (Roll No !""!#$$$%& is hereby approved for submission

'rof ()* (Supervisor& +ate, "!-!-%$!!" 'lace, .umbai

"EC)#R#$!&N
/ declare that this 0ritten submission represents my ideas in my o0n 0ords and 0here others1 ideas or 0ords have been included, / have ade2uately cited and referenced the ori3inal sources / also declare that / have adhered to all principles of academic honesty and inte3rity and have not misrepresented or fabricated or falsified any idea-data-fact-source in my submission / understand that any violation of the above 0ill be cause for disciplinary action by the /nstitute and can also evoke penal action from the sources 0hich have thus not been properly cited or from 0hom proper permission has not been taken 0hen needed

Smarika Kulshrestha Roll No, !""!#$$$% !ate" 31#10#2013

#C/N&0)E"*E-EN$
/ 0ould like to e4press my sincere thanks and 3ratitude to my 3uide 'rof Suparna .ukher5ee for all the 3uidance in this seminar / am thankful for the efforts taken by her to supervise me throu3hout the pro5ect and make necessary su33estions and corrections as and 0hen needed / am also thankful to .iss Sharda 6harti for her assistance durin3 the literature revie0

Smarika Kulshrestha

#,S$R#C$
Nanomaterials are diverse class of small7scale substances 0ith structural components 0ithin nanometre ran3e Nanomaterials can be cate3ori8ed into three ma5or classes, natural, incidental and en3ineered En3ineered nanomaterials 0ith desi3ned properties are bein3 used in a 0ide variety of applications includin3 environmental remediation, pollution sensors, photovoltaics, medical ima3in3 and dru3 delivery 9ithin a decade or t0o there has been a lar3e increase in the number of nanomaterials used in commercial and industrial applications These nanoparticles may be released in the environment throu3h point or non7point sources, incidentally or for the purpose of environment remediation 6ecause of the small si8e of the nanoparticles, they are readily transported throu3h media, over much lar3er distances than lar3er particles of same composition The nanoparticle mobility depends on their surface chemistry and particle si8e alon3 0ith other factors and interaction in media Nanoparticles may stay in suspension as individual particles, a33re3ate, dissolve or react 0ith natural materials in the environment :nderstandin3 the behaviour and effects of nanoparticles is important in the conte4t of increasin3 applications of nanoparticles in various fields So far, scientific evidences sho0 that certain nanoparticles have to4ic effects under lab conditions, but under actual environmental conditions nothin3 much is kno0n about the behaviour of nanoparticles Thus, there is a need for research on interaction bet0een nanoparticles and environmental components (0ater, sediments and soil&, and ecoto4icity studies of nanoparticles to completely understand the fate and environmental effects of nanoparticles The present report is a revie0 of the scientific kno0led3e on the characteristics, transport mechanisms, fate and effect of nanoparticles released into the environment

C&N$EN$S
#pproval S1eet.........................................................................................................................iii "EC)#R#$!&N.....................................................................................................................iv #c2no3led ement....................................................................................................................v v #bstract.....................................................................................................................................vi Contents...................................................................................................................................vii )ist of 'i ures........................................................................................................................viii )ist of $ables..........................................................................................................................viii

!ntroduction ......................................................................................................................4

Nanoparticles: *eneration and C1aracteristics ............................................................5

'ate and &ccurrence of Nanoparticles in Environment..............................................46

Environmental Effects of Nanoparticles ......................................................................78

Conclusions......................................................................................................................79 References................................................................................................................................8:

)!S$ &' '!*%RES

'i ure 4.4 : Nanomaterial releases to t1e environment (0eisner et al.+ 7::;)....................8 'i ure 7.7 'ullerenes of different si<e and an endo=fullerene containin )ant1anum.....44 'i ure 7.8 (a) *rap1ene S1eet> (b) S0CN$: Sin le 0alled Carbon Nanotube> (c) -0CN$: -ultiple 3alled Carbon Nanotube (/reupl et al.+ 7::?)...........................47 'i ure 7.? *eneral reactivit@ trend associated 3it1 particle si<e ......................................45 'i ure 8.5 -aAor t@pes of a re ates formed in t1e t1ree=colloidal component s@stem..74

)!S$ &' $#,)ES

$able 4 Classification+ Properties and %ses of Nanoparticles...............................................B

!ntroduction

1.1 Background

Nano si8ed particles have been present on earth and have been in use by mankind from millions of years E 3 soot is a naturally occurrin3 nanoparticle 0hich is produced by incomplete combustion of fossil fuels and ve3etation (No0ack and 6ucheli, %$$;& Recently there has been an increase in usa3e of nanomaterials in areas such as electronics, biomedical, pharmaceutical, cosmetic, ener3y, environment, catalysis and material application because si3nificant advancements have been made in synthesis and desi3n of nanomaterials as per our re2uirements for 0ide variety of industrial and consumer products (9eisner et al , %$$<& = hu3e increase in the manufacture and use of nanomaterials has been forecasted and 0ith that the area of ne0 nanomaterials is believed to be ne4t revolution in technolo3y development after /nformation Technolo3y (9it, %$$>& Nanotechnolo3y and nanomaterials has been a prime area of research and development for 2uite a fe0 years no0 and more research is still 3oin3 on in this field =s the fundin3 and research in this area be3an to 3ro0, researchers be3an ponderin3 about potential risks that these ne0 products may pose on humans and on the environment (?olvin, %$$"& The research for environmental implications of 3reater use of nanomaterials be3an 0ell in time, learnin3 from the past scenarios, such as the introduction of or3ano7chlorine pesticide Earlier, ++T 0as introduced 0ithout much understandin3 of its environmental risks and associated environmental problems 0hich after0ards caused a 3reat loss to ecolo3y and environment Research on both positive effects as 0ell as associated ne3ative effects of nano7technolo3y is bein3 conducted This in turn can minimi8e the harmful impacts the technolo3y can have on environment and this is also to improve the public acceptance of this technolo3y The case 0ith biotechnolo3y application has been seen 0here there 0as a lack of public acceptance because of discountin3 of environmental implications of the technolo3y Risk assessment for nanotechnolo3y has been a cause of concern since the be3innin3 of technolo3y development alon3 0ith the innovation and application related researches for nanoparticles @o0ever,

it is difficult to predict the environmental effects in the very infancy of a technolo3y .ore than !<$$ nanomaterial containin3 products are in the market today (99/?, %$!"&, after more than %$ years of basic and applied research in the field of nanotechnolo3y This sho0s an increasin3 commercialisation of nanotechnolo3y These products include cosmetics, personal care products, clothin3 and sportin3 3oods .a5or nanomaterials involved are silver, follo0ed by carbon, 8inc, titanium and silicon Nano7silver is bein3 used as a bactericide in banda3es, clothin3, cuttin3 boards and food containers (9it, %$$>& The use of these nanomaterials may lead to direct dischar3e into atmospheric and 0aste 0ater systems and conse2uently to a2uatic systems Studies have sho0n that "<7A#B of the nanomaterial containin3 products in the market can pose risk due to direct e4posure on human bein3s (@ansen et al , %$$#& The appearance of nanomaterials in 0ater, soil and in various or3anisms is inevitable 0ith their use (9eisner et al , %$$<& as is sho0n in Fi3 ! ! /n the environment, nanoparticles are released from point and non7point sources from various types of processes employin3 and 3eneratin3 them =fter0ards they under3o different types of processes such as a33re3ation, bio7transformation, accumulation, photolytic reaction or de3radation in or3anisms Transport of nanoparticles occurs throu3h mediums such as 0ater or air The nanoparticles in surface or 3round 0ater are sub5ected to treatment processes such as coa3ulation, flocculation and filtration, simultaneously durin3 0ater treatment @ence it is important to determine the removal characteristics of nanomaterials in such processes @umans can also 3et e4posed to nanoparticles throu3h inhalation, in5estion, or dermal contact of nanomaterial containin3 products (Tran et al , %$$A&

'i ure 4.4 :

Nanomaterial releases to t1e environment (0eisner et al.+ 7::;)

To understand the effects of nanoparticles dischar3ed into the environment, it is necessary to understand the various processes 0hich 3enerate or involve nanoparticles, the chemical composition, nature and behaviour of nanoparticles, 2uantity of nanomaterials dischar3ed, the transport mechanisms involved and fate of nanoparticles in environment The fate and transport of nanomaterials in the environment is a function of material properties such as surface chemistry, particle si8e, and biolo3ical and abiotic processes in environmental media (Cuoma, %$$#& Research has been 3oin3 on to find the effects of nanoparticles on the environment, ho0 various parameters can be chosen to describe the fate and transport, and 2uantification of nanoparticle properties

1.2 Objectives of Literature Survey

The ob5ective of this survey report is to revie0 the research and obtain an understandin3 re3ardin3 the follo0in3 areas,

! %

Nanomaterials, their sources and classification Structure 7 activity relationship for different types of nanoparticles

" Nanomaterial fate and transport in the environment D Environmental risks associated 0ith the nanomaterials and possible control measures

1.3 Organisation of Report

The present report is arran3ed into five chapters The first chapter is a brief introduction to the field of nanotechnolo3y and the environment implications of the use of nanoparticle containin3 products /n the second chapter the sources and characteristics of nanoparticles are described /n the third chapter, the details of various transport mechanisms of nanoparticles released in the environment and the factors affectin3 the fate of nanoparticles in the environment are discussed Fourth chapter presents the effects various nanoparticles may have on the environment Fifth chapter presents the conclusions this literature survey

Nanoparticles: *eneration and C1aracteristics

Nanomaterials (N.s& are a diverse class of small scale substances that have structural component smaller than !micrometer (!$$$ nanometres& in at least one dimension N.s include nanoparticles (N's& 0hich are particles 0ith at least % dimensions bet0een appro4imately ! to !$$nm in Nano scale (E'S, %$$#aE Cuoma, %$$#& They can be of various shapes F spherical, tubular or irre3ular shapes The colloidal fraction is defined as havin3 si8e bet0een !nm and !Gm (6uffle, %$$<&, therefore there is some overlap 0ith the Nanoparticle si8e ran3e

1.4 C assification of !anopartic es

Nanomaterials can be classified into the follo0in3 three cate3ories accordin3 to their sources (E'=, %$!$&, Natural nanoparticlesE /ncidental nanoparticles and En3ineered nanoparticles =n elaborate description has been sho0n in the Table!, 0ith the physical and chemical properties, uses and e4amples Natural nanoparticles e4ist on earth from the time it 0as formed (6uffle, %$$<& Natural nanoparticles includes or3anic (carbon7containin3& and inor3anic (0ithout or3anic carbon& nanoparticle1s .ost common e4amples are soil colloids 0hich are composed of clay minerals, iron or aluminium o4ides-hydro4ides or humic or3anic matter includin3 black carbon (soot& =lso airborne e4amples are nano7crystals formed from sea salt as a result of sea 0ater spray /ncidental nanoparticles are of t0o types, anthropo3enic (from 3rindin3 of primary or secondary minerals, 0ear of metal or mineral surfaces and combustion& and pyro3enic ori3in (smoke from volcanoes or fires& (Honer et al , %$$;& En3ineered Nanoparticles (EN's& are the particles that are produced by man because these particles possess specific desi3n properties Iarious en3ineered nanoparticles have been desi3ned so far and research is still 3oin3 on to

3et improved properties of nanomaterials for a 0ide ran3e of applications En3ineered particles are often classified on the basis of their chemical composition (Honer et al , %$$;& si8e or morpholo3ical characteristics ?lasses of EN' as sho0n in Table % ! are based on E'= %$$# (E'=, %$$#E Cuoma, %$$#&

$able 4 Classification+ Properties and %ses of Nanoparticles $@pes of Nano=materials $arbon%based &'atural or (n)ineered* &(+, 200-. Klaine et al/ 2008* ECamples 0ullerenes#1uckyballs &$arbon 20 $arbon 20 $arbon -0*. carbon nanotubes. nanodiamonds. nano3ires/ P1@sical Properties 4hese e5ist as hollo3 spheres &buckyballs* ellipsoids tubes &nanotubes*. 1nm 3ires &nano3ires* or he5a)onal structures &nanodiamonds*/ (5cellent thermal and electrical conductivity/ 6etal O5ides &'atural or (n)ineered* &Klaine et al/ 2008* 4itanium dio5ide &4iO2*. 7inc o5ide &8nO*. cerium o5ide &$eO2*/ Some have photocatalytic properties and some have ultraviolet &U9* blockin) ability/ :hen used in sunscreen nano%4iO2 and nano% 8nO ;i)h reactivity. photolytic properties/ +hotocatalysts pi)ments dru) release medical dia)nostics U9 blockers in sunscreen diesel fuel additive and remediation/ C1emical Properties $arbon%based '6s are stable have limited reactivity are composed entirely of carbon and are stron) antio5idants/ %ses 1iomedical applications super% capacitors sensors and photovoltaics/

$@pes of Nano=materials

ECamples

P1@sical Properties

C1emical Properties

%ses

appear transparent 3hen applied on skin/

'anosilver &(n)ineered* &Klaine et al/ 2008. <uoma 2008*

0orms include colloidal silver spun silver nanosilver po3der and polymeric silver/

Si7e" 10 to 200 nm/ 6ade up of many atoms of silver in the form of silver ions/

;i)h surface reactivity. stron) antimicrobial properties/

6edicine applications 3ater purification and antimicrobial uses/ 4hey are used for a 3ide variety of commercial products/

!endrimers &(n)ineered* &(+, 200-. :atlin)ton 200=*

;yperbranched polymers dendri)raft polymers and dendrons/

Si7e" 2 to 20 nm/ ;i)hly branched polymers/ $ommon shapes include cones spheres and disc%like structures/

;i)hly branched. multi% functional polymers/

!ru) delivery chemical sensors modified electrodes and !', transferrin) a)ents/

$@pes of Nano=materials

ECamples

P1@sical Properties

C1emical Properties

%ses

>uantum !ots &(n)ineered* &Klaine et al/ 2008*

>uantum dots made from $admium Selenide &$dSe* $admium 4elluride &$d4e* and 8inc Selenide &8nSe*/

Si7e" 10 to =0 nm/ Reactive core controls the material?s optical properties/ 4he lar)er the dot the redder &lo3er ener)y* its fluorescence spectrum/

$losely packed semiconductor 3hose e5citons &bound electron%hole pairs* are confined in all 3 spatial dimensions/ +ossible metal structures include" $dSe $d4e $dSe4e 8nSe @n,s or +bSe for the core. $dS or 8nS for the shell/

6edical ima)in) photovoltaics telecommunication and sensors/

$omposite '6s &(n)ineered* &(+, 200- Ail B +arak 2008*

6ade 3ith t3o different '6s or '6s combined 3ith nanosi7ed clay/ 4hey can also be made 3ith '6s combined 3ith synthetic polymers or resins/

$omposite '6s have novel electrical ma)netic mechanical thermal or ima)in) features/

6ultifunctional components. catalytic features/

+otential applications in dru) delivery and cancer detection/ ,lso used in auto parts and packa)in) materials to enhance mechanical and flame%retardant

$@pes of Nano=materials

ECamples

P1@sical Properties

C1emical Properties

%ses

properties/

8ero%9alent 6etals (n)ineered* &(+, 2008a. Klaine et al 2008*

'anoscale 7ero%valent iron 1et3een 1 to 100 nm or &n89@* emulsified 7ero%valent iron &(89@* and bimetallic nanoscale particles &1'+s*/ 1'+s include elemental iron and a metal catalyst &such as )old nickel palladium or platinum* )reater dependin) on the '6%type containin) the 7ero% valent metal/ +roperties can be controlled by varyin) the reductant type and the reduction conditions/

;i)h surface reactivity/ +opular startin) materials used in production include" ferric &0e C@@@D* or ferrous &0e C@@D* salts 3ith sodium borohydride/

Remediation of 3aters sediments and soils to reduce contaminants such as nitrates trichloroethene and tetrachloroethene/

1." Overvie# of $ngineered !ano%&artic es

The composition and properties of en3ineered nanoparticles influence their behaviour in the environment +ifferent types of en3ineered nano7 particles and their properties have been described in the section

1.".1 'u erenes

These are nanomaterials made up of pure carbon Fullerenes 0ere discovered in !>#A and are an allotropic form of carbon The simplest form of fullerene is ?<$ /t is like a ball made up of <$ carbon atom and resembles a football (fi3ure % !& These are also kno0n as 6uckminster fullerenes or bucky balls, after the architect Richard 6uckminster fuller 0ho constructed a ran3e of 3eodesic sphere and domes 0ith fullerene resemblin3 structures =nother fullerene ?;$ is less stable than ?<$ and has an oblon3 form Jther fullerenes are ?;D, ?;<, ?;#, and so on ?arbon7nanotubes are formed by fullerenes 0hen they are 3ro0n by vapour deposition Fullerenes are hydrophobic and are only soluble in or3anic solvents =n atom, ion or small cluster may 3et trapped inside the fullerene shell to form 0hat is called endo7fullerene =t the surface of fullerenes, functional 3roup can attach covalently to a carbon atom, leadin3 to a functionalised surface formation @ydro4ylation is a commonly occurrin3 functionali8ation (attachin3 J@7 3roups& @ydro4ylated fullerene is called fullerol @ydro4ylation can make the molecule more hydrophilic (6rant et al , %$$;b& Fullerenes also may form hi3hly stable hydrophilic nano7si8ed a33re3ates (e 3 n?<$& in !$$7%$$ nm particle diameter ran3e These a33re3ates e4ist in stable a2ueous suspensions at lo0 ionic stren3th

'i ure 7.7

'ullerenes of different si<e and an endo=fullerene containin )ant1anum.

Image from http://www.photon.t.u-tokyo.ac.jp/

1.".2 Carbon !anotubes (C!)s*

These are fibrous fullerenes These consist of rolled up 3raphene sheets 0hich are planar layers of carbon atoms that may or may not be capped at the ends by half fullerene spheres Nanotubes can be sin3le, double, or multiple 0alled, respectively called as sin3le 0alled carbon nanotubes (S9?NTs&, and double 0alled carbon nanotubes (+9?NTs& and multiple 0alled carbon nanotubes (.9?NTs& Kraphite is used as a startin3 material for ?NTs 0hich are produced by laser ablation of 3raphite The uni2ue property of ?NTs is that they are li3ht and possess very hi3h mechanical stren3th =lso they possess specific conductive properties, 0hich is a function of symmetry of ?7? bonds (fi3ure % %& ?NTs are useful as semiconductors in electronics and a 0ide ran3e of other applications Research is 3oin3 on in the production of ?NTs, purification and separation of different types of ?NTs S9?NTs are believed to have improved mechanical stren3th, thermal and electrical conductivity over .9?NTs

'i ure 7.8

(a) *rap1ene S1eet> (b) S0CN$: Sin le 0alled Carbon Nanotube> (c) -0CN$: -ultiple 3alled Carbon Nanotube (/reupl et al.+ 7::?)

?NTs are hydrophobic and in the form of fibres, thus they can easily a33re3ate and form bundles termed as Nano7fibres, Nano7ropes and nano7 0ires, dependin3 upon their dimensions Nano fibres are short and thin, 0hereas Nano ropes and nano0ires are thicker and lon3er up to millimetre scale

1.".3 Carbon B ack

?arbon 6lack (?6& is present as soot, and is one of the oldest nanoparticles in nature /t is a by7product of combustion, therefore occurs naturally durin3 fires /t has been in use by industries for many years /t is a ma5or constituent of tyres of cars /t is used as filler in tyres accountin3 for up to "$B of mass ?6, like fullerenes or ?NTs is composed of 3raphene fra3ments These are very resistant to de3radation and thus, can accumulate in the environment ?6s have been used as a reference substance in to4icity studies of ?NTs and fullerenes (?han3 et al , %$$;&, possibly because of the reason that they are more fre2uently occurrin3 in nature than the latter t0o

1.".4 +%,ots

Luantum +ots or L7+ots are fluorescent semiconductor nano7crystals They contain a core of ?dS, ?dSe, 'bSe, ?d@3 or a ran3e of other metals, "7< nanometre in diameter coated by an or3anic polymer 0hich protects them a3ainst o4idation and permits linkin3 to biolo3ically active moieties like antibodies L7+ots have a very small si8e, 0hich is smaller than 6ohr e4citon radiusE therefore they can emit li3ht, i e photons 0ith a specific 0avelen3th, 0hich is determined by 2uantum confinement and determined by particle si8e and composition (i e resultin3 band 3ap ener3y& L7+ots are used in biolo3y and medicine for fluorescence ima3in3 to locali8e specific cells like tumour cells (.ichalet et al , %$$A&

1."." Ot-er .inera nanopartic es

= lar3e number of nanoparticles e4ist in mineral forms These have variable particle si8es and different preparation methods =lso they may be used in different types of surface coatin3s E4amples of Sin3le element Nanoparticles are =3, =u, ?u, and Fe ?ompound Nanoparticles include Si? and Nanoparticles can be sin3le metal o4ides like and SrTi , Ti and

*nJ or multi metal o4ides e 3 .3

Jther type of Nanoparticles encountered in literature is n*I/ or FeM that is 8ero valent iron and nano7clays These are composed of mineral nanoparticles and are involved in recent research and development processes *ero valent iron is used as a33re3ates of Fe-Fe o4ides 0ith hi3h internal surface or or3anic coated particles These particles are e4ploited for absorption of various environmental pollutants in soil and 0ater, e 3 arsenic Nano7clays are chemically and mechanically dispersed clay minerals Natural clays e4ist as a packa3e of Nano si8ed layers 0ith %7A$ nm of thickness of silica, aluminium or iron o4ides These nano layers possess useful properties, like impermeability to 3as, that can be e4ploited in applications like improvin3 stora3e of food and other easily de3radable substances (=vella et al , %$$A& En3ineered nano particles that contain or3anic carbon are of little concern for potential environmental impact because they are composed of de3radable polymers They have a short life span once they enter the environment Their preparation processes and composition is also such that little or no harm is posed to livin3 or3anisms EN's such as liposomes, micelle or dendrimer transport ca3es have been developed for pharmaceutical products These nanoparticles are de3raded once the dru3 is delivered to the tar3et tissue 6iode3radable plastic films use or3anic en3ineered nano7particles that are based on Starch polymers

1./ C-aracterisation of !anopartic es

To be able to compare the results from different researchers, it is important to have a 3ood characterisation basis of nanoparticles /t is also necessary to find a correlation bet0een the characteristics of nanoparticles and their behaviour and effects in the environment Iarious studies have been done in this field, but there is still re2uirement of 3lobal descriptors 0hich provide an appropriate yet stron3 basis for comparison bet0een different nanoparticles and at the same time provide a 3ood insi3ht of fate of nanoparticles and their effect on environment ?haracterisation of nanoparticles is particularly difficult because these materials falls into a 3rey area, 0here in many cases, they may behave either as small particles or as lar3e solutions Some of the important characteristics that are used to describe EN's are discussed in this section These characteristics can be used for determination of fate and to4icity of nanoparticles (Rose et al, %$$;& 'hysical characteristics that are used to describe nanoparticles are particle si8e, surface area and crystalinity +e3radability or persistence, elemental composition, surface

char3e and 'oint of 8ero char3e ('*?& are chemical parameters that are used to describe nanoparticles

1./.1

&-ysica C-aracteristics

Nanoparticles are hi3hly mobile and reactive pertainin3 to their si8e (@arland et al , %$!"& =s particles 3et smaller and smaller their surface area increases in comparison to their volume and 3ives rise to their enhanced reactivity The chan3es in the reactivity of nanoparticles are due to their si8e and electronic properties (.adden et al , %$$<& = 3enerali8ed particle si8e7activity relationship is sho0n in Fi3ure % " (9i33inton et al , %$$;&

'i ure 7.?

*eneral reactivit@ trend associated 3it1 particle si<e (Wigginton et al., 2007

Since a cluster of EN's is not homo3eneous in si8e, the terms used to characteri8e them are avera3e particle si8e (='S&, effective particle si8e (E'S&, avera3e a33lomeration number (==N&, and aspect ratio The morpholo3y of pure nanomaterials is 3enerally described usin3 hi3h resolution scannin3 electron microscopy (@R7SE.& or hi3h resolution transmission electron microscopy (@R7TE.& These methods can be used to directly visuali8e nanoparticles @R7SE. can be used for particles as small as !$7%$ nm, 0hile @R7TE. can have a resolution belo0 !nm Jther methods like atomic force microscopy (=F.& and scannin3 tunnel microscopy (ST.& have resolution do0n to atomic level, and permit three dimensional ima3in3 of nanoscale particles For commercially available nanoparticles, avera3e particle si8e is provided by the manufacturer for certain nanoparticles /n the case of fullerenes, the diameter is 3overned by the number of atoms that they contain (e 3 $ ;nm is the si8e of ?<$& =lso sin3le 0alled ?NTs have a narro0 ran3e of diameters (!7"nm&, but variable len3th =lso some nanoparticles have a tendency to cluster in a li2uid so to keep them in a suspended form, surfactants or other coatin3s are added These additives stabili8e the suspension by creatin3 an envelope around the particles This envelope increases the si8e of nanoparticles such that the ne0 si8e i e the effective si8e is more than the avera3e particle si8e /f nanoparticles a33re3ate, they no further behave as individual nanoparticles Thus their si8e is measured as a33re3ate si8e =vera3e a33lomeration number (==N& is an estimate of the de3ree of a33lomeration in a suspension =nother term, aspect ratio, is defined as the ratio bet0een the lar3est diameter of a particle and the smallest perpendicular diameter /t is one of the important parameters that determine the shape of a particle /t can have an effect on the si8e7activity relationship of particle Nanoparticle surface area can be most reliably determined as 6ET surface area, based on theoretical model for 3as adsorption developed by 6runauer, Emmet and Teller published in !>"# Total surface area includin3 the e4ternal and internal surfaces of a nanoparticle is important to determine the surface area F activity relation of a nanoparticle =ll interaction bet0een nanoparticles and the surroundin3 medium occurs throu3h the surface Specific surface area is the ratio of surface area to the volume The activity of nanoparticles increases 0ith increase in specific surface area i e decreasin3 particle si8e The "7+ crystal structure in 0hich atoms are arran3ed, also affect their properties /t can have several direct or indirect effects on chemical and morpholo3ical parameters like surface area, char3e and aspect ratio

1./.2 C-e.ica C-aracteristics

Elemental composition is a description of 0hat elements compose the nanoparticles /t can be usin3 standard chemical analysis, like /?'7.S (/nductively coupled plasma mass spectrometry& For en3ineered nanoparticles, their purity and ma5or contaminants are 3enerally 2uoted by manufacturers ?hemical composition of nanoparticles affects their de3radability and persistence in the environment Jr3anic nanoparticles are biode3radable but allotropes of carbon are e4tremely persistent .inerals nanoparticles may under3o dissolution reaction or 0eatherin3 in the environment Surface of nanoparticles can possess char3e 0hich is dependent on p@ of the solution or it may be a result of crystal lattice defects and atomic substitution (Rose et al , %$$;& /n latter case, the char3e is fi4ed and independent of p@ of solution Surface char3e affects the properties such as reactivity and hydrophobicity, 0hich describe particle1s capacity to interact 0ith 0ater Surface char3e and hydrophobicity are important factors 0hich determine nanoparticles behaviour in environment = char3ed nanoparticle under3oes motion 0hen an electric field is applied /f p@ is varied, the surface char3e of nanoparticles chan3es dependin3 upon the concentration of or ions in the medium 'oint of 8ero char3e ('*?& is the p@ at 0hich the positive and ne3ative char3es are balanced so that there is no net char3e on the particle, makin3 it immobile in the electric field :sin3 more sophisticated e2uipment, other parameters may also be determined e 3 chemical structure, surface properties usin3 nuclear ma3netic resonance (N.R& (Rose et al , %$$;& There is a lack of tools to detect and 2uantify nanoparticles in natural 0aters, sediments, soil, 0aste, and se0a3e slud3e This is a ma5or constraint to describe fate, e4posure and risks associated 0ith the spread of nanoparticles in environment Research has been 3oin3 on to improve the characterisation of nanoparticles, so that their subse2uent effects on environment can be predicted

'ate and &ccurrence of Nanoparticles in Environment

1.0 Background

To assess the risk imposed by the use of nanomaterials in commercial products and environment applications, a better understandin3 is re2uired in term of their mobility, bioavailability and to4icity /n 3eneral to study the risk associated 0ith nanoparticles, the e4posure probabilities and ha8ard caused by them, both have to be studied The e4posure probabilities can be understood by studyin3 the occurrence of nanomaterials in environment

1.1 2ove.ent of !anopartic es

The production, utilisation and inade2uate treatment of Nanomaterials containin3 products inevitably leads to the culmination of nanoparticles in the environment (No0ack and 6ucheli, %$$;& To assess the impact of nanoparticles pollutants endin3 up in the environment, three aspects seems to be important (Honer et al , %$$;& ! Transfer and Transport F it is defined as the ability of N'S to move from one place to other (e 3 from contaminated site to uncontaminated site& or from one medium to other (e 3 from soil to drinkin3 0ater or food plants& % Ecoto4icity F The harms associated 0ith e4istence of nanoparticles in the ecosystem is called ecoto4icity /t includes 0hat possible harm nanoparticles can cause to or3anisms livin3 in the ecosystem

" .odification F Jnce Nanoparticles are released in the environment, they may under3o certain modification This modification can be result of nanoparticle interaction 0ith environmental components and can have conse2uences that may affect ecoto4icity and mobility

1.3 )ransport 2ediu.s

Jnce the nanoparticles are released to the environment, they travel throu3h the air, 0ater or soils @umans and other or3anisms may come in contact 0ith EN's throu3h these mediums The nanoparticles travellin3 throu3h air can a33re3ate and become bulkier, thus can settle do0n by 3ravity in the environment /n this case, the ultimate recipient for non7 volatile compounds 0ould be sediments or soil +etailed descriptions of mediums throu3h 0hich nanoparticles can travel are discussed in the section

1.3.1 Soi

Soils and sediments include constituents such as clay and or3anic matter 0hich have lar3e surface area and form a porous media These particles also have a hi3h surface char3e so that they can interact 0ith char3ed particles like many en3ineered nanoparticles Natural or3anic matter comprises of t0o types of constituents, non7humic substances and humic substances Non7humic substances are primary components that are inherited from plants and animals residues enterin3 the soil e 3 polysaccharides, amino acids, carbohydrates and lipids (J?, %$!"& 0hereas humic substances comprise of or3anic macromolecules that are formed by partial de3radation and transformation of recalcitrant plant and microbial polymers (@S, %$!"& Soluble humic substances are basically fulvic acids and humic acids Fulvic acids are humic substances that are 0ater soluble at all p@, 0hereas humic acids are defined as humic substances that are insoluble at lo0 p@ of about less than %, but soluble at alkaline p@ A$B of natural matter in sediments are composed of humic and fulvic acids (Hones and 6ryan, !>>#& Nanoparticles in the environment occur in a 0ide si8e ran3e 0hich may cover even the colloidal particle ran3e These can be formed as a result of breakdo0n of humic substances, non7humic substances and other minerals that are 3enerated durin3 chemical 0eatherin3 of rocks e 3 o4ides and o4y7hydro4ides of iron (Fe&, man3anese (.n& and aluminium

(=l& and alumino7silicates (@artland et al , %$!"& @umic substances can e4ist as dispersed materials 0ith si8e less than Anm, and can also a33re3ate to form layer structures 0hich can reach dimensions outside the nano7ran3e

1.3.2 4ater

9ater can e4ist as natural 0ater in lakes and streams or as pore 0ater in sediments and soil This 0ater contains natural colloids and dissolved ions +ispersed colloids are particles in N' ran3e (!7%$$nm& that remains in a stable suspension in 0ater They do not precipitate by 3ravitation due to their small si8e and surface char3e that enables them to maintain stable suspension This suspension can be altered by variation of p@ or ionic concentration =ccordin3 to classical double layer and colloid stability theories (J1 .elia, !>;%&, if the salt concentrations are increased free nanoparticles start to a33re3ate Jr3anic matter in 0ater includes peptides, proteins, peptido3lycans and similar biomolecules

1.15 )ransport 2ec-anis.s

9ater, to a lar3e e4tent serves as transport medium Throu3h 0ater, Nanoparticles may 3et transported in the dissolved and suspended form .ost nanoparticles do not dissolve ho0ever, they may 3et adsorbed on other surfaces Suspended particles serve as adsorbents for nanoparticles These particles can under3o various processes such as, Kravitational settlin3E separation throu3h interception or settlin3 throu3h diffusion (J1 .elia, !>;!& 9hen the particle si8e is very small, nanoparticles are not very mobile because of their very hi3h diffusivity 0hich promotes contact 0ith other surfaces and subse2uent deposition on the surface The phenomenon of deposition involves particle deposition on an immobile contact surface =33re3ation is a similar phenomenon 0here contact surface is mobile These smaller particles eventually tend to form a33re3ates or 3et deposited The physics of particle transport for spherical particles is very 0ell understood and is used for various models @o0ever predictin3 the transport of particle 0ith comple4 surfaces is difficult /t re2uires simplifyin3 assumptions and ne0, previously unconsidered factors (9eisner et al , %$$<& 'ractical approaches usin3 simplified model system are used for the study of attachment and transport of EN's Jne such approach 0as modelled usin3 e4periment 3lass beads or 2uart8 sand as

the solid phase and pure 0ater as transport medium The main mechanisms that 3overn the mobility of nanoparticles in porous media have been described and 2uantified throu3h e4perimental studies Cecoanet et al (%$$D& 0ere the first to study mobility of EN' in porous media They studied the mobility of three types of fullerenes (fullerol, n?<$ and S9?NTs&, Ti and Si at t0o different flo0 rate usin3 columns packed 0ith 3lass beads =fter0ard many authors, 0ith a lar3er ran3e of en3ineered nanoparticles conducted similar e4periments, also includin3 alumo4ane, lar3e silica nanoparticles and fero4an, in addition to A EN'S from previous e4periment (Cecoanet et al , %$$D& They compared the mobility of different nanoparticles and found that lo0est mobility in this e4periment 0as observed for n?<$, 0hereas hi3h mobility i e !$$ times that of n?<$ 0as found for fullerol and surfactant based S9?NTS Stability of a suspension determines the movement of solutes /f the solution is stable, the nanoparticles 0ill remain suspended in solution /n an unstable solution, nanoparticles 0ill a33re3ate to3ether and deposition 0ill result (Kimbert et al , %$$;& (Fi3ure " %& Several factors can affect the stability of suspension, includin3 surface potential, p@ chan3es, increase in ion concentration, dilution or de3radation of stabli8in3 a3ents (Surfactant or coatin3&

'i ure 8.5

-aAor t@pes of a

re ates formed in t1e t1ree=colloidal component s@stem

!ul"ic compoun#$ (!% - $mall point$& inorganic colloi#$ (I% -circle$& rigi# 'iopolymer$ -line$. (oth !% an# poly$acchari#e$ can al$o form gel$, which are repre$ente# a$ grey area$ into which I% can 'e em'e##e#. The movement of nanoparticles throu3h the soil depends upon the porosity, surface char3e and reactivity of medium and the prevailin3 physical7chemical conditions Soil behaves like a comple4 porous media Filterin3 conditions occur in soil matri4 0hich 3overns the fate and behaviour of nanoparticles dispersed in these systems (Ryan and Elimelech, !>><& /t is difficult to understand the transport and fate of nanoparticles under the natural conditions because it has to take into account the or3anic and mineral composition and structural hetero3eneity of the media Iery less is kno0n about ho0 EN's interact 0ith soil and sediments (Jberdorster et al , %$$<E 9eisner et al , %$$<& Soils, sediments and 0ater bodies contain solids and dissolved matter 0hich can act as po0erful 3eo7 sorbents Some nanoparticles such as fullerenes and carbon nano7tubes (?NT& are non7polar and do not easily disperse or dissolve in 0ater, similar to or3anic contaminants like polycyclic aromatic hydrocarbons ('=@s& Environmental factors like p@ and ionic stren3th (6rant et al , %$$Ab& to3ether 0ith physical7chemical properties, structure and concentration of nanoparticle may determine 0hether nanoparticles are transported in or out of the soil and sediments +J. (dissolved or3anic matter& present in both surface and soils 0ater, has been sho0n to interact 0ith ?NTs in a 0ay that may enhance their dispersion and transport (@ycen3 et al , %$$;&

1.11 Ot-er 6spects 6ffecting t-e 'ate of !anopartic es

Redo4 reactions can also influence the transformation and fate of nanoparticles (9iesner at al , %$$<& Redo4 reactions are one of the most common reaction in the environment and they play a role in de3radation of or3anic matter, ener3y 3eneration reaction, precipitation and dissolution reaction Nanomaterials may 3et transformed due to the redo4 processes in the environment Research is 3oin3 to study ho0 and to 0hat e4tent, the transformation of nanoparticles take place The environment impact of nanoparticles is mostly attributed to their, de3radability or persistence, in environment 'ersistent particles 0ith ne3ative effects are more harmful as they 0ill stay lon3er in the environment ?7based nanoparticles like fullerenes and ?NTs are e4pected to be de3radable @o0ever it has been found that ?NTs and fullerenes are

e4tremely persistent to the hi3h temperatures, stron3 acids, and photolytic-o8onation attack Therefore they are more likely to accumulate in the environment .inerals nanoparticles are prone to 0eatherin3 and dissolution and de3rade 0hen they are e4posed to environmental conditions Jr3anic 'olymers7based and polymer like nanoparticles such as starch derivative, and dendrimers are hi3hly biode3radable 9hen EN's are used in medical applications, the transporter ca3e is de3raded, releasin3 the pharmaceutical content after reachin3 the tar3et tissue

Environmental Effects of Nanoparticles

1.12 )o7icity and $coto7icity Considerations

The t0o terms to4icity and ecoto4icity have different meanin3s To4icity focuses on human bein3s and tar3ets at protectin3 individuals Ecoto4icity looks at to4icity to or3anisms at various trophic levels To4icolo3y usually evaluates adverse effects of a compound once it is absorbed by an or3anism, 0hile ecoto4icity includes natural uptake mechanisms and the influence of environmental factors on bioavailability, and thereby on to4icity = dry, dispersed nano7po0der infused directly into the respiratory tract of an animal possibly can stimulate a ma4imum of adverse effects, 0hereas, the same particles mi4ed into river 0ater rich in salts, clay and or3anic matter may not be available to be absorbed by the 3ills of a fish or the filterin3 apparatus of a mussel 6efore they reach such absorbin3 or3ans, they may have a33re3ated or interacted 0ith other particles or solutes so that they become far less reactive and possibly even entirely unavailable for biolo3ical absorption = lar3e amount of nanoparticles is present in the atmosphere, e 3 carbon nanotubes and other fullerenes (.urr et al , %$$D& = lot is already kno0n about 0hat happens 0hen nanoparticles deposit in air0ays and lun3s of mammals The adverse effects that are caused include o4idative stress, inflammation and cardiopulmonary diseases (@andy and Sha0 , %$$;E Jbersdorster et al , !>>A& The uni2ue 2ualities of nanoparticles, includin3 si8e, lar3e specific surface area, reactivity and shape make them suitable for technolo3ical applications These 2ualities at the same time, makes it

likely for these particles to enter or3anisms and travel throu3h tissues, cells and even to cell or3anelles, 0hich is not possible for lar3er particles (Kovochich et al , %$$;& Thus different studies involvin3 both in7vitro and in7vivo measurements have come out 0hich can address the to4ic effects of nanoparticles /n7vitro tests are 3enerally sou3ht since it is ethically dubious to perform in7vivo e4periments involvin3 animals and these are tried to be ad5usted for in7vivo outcomes These in7vitro studies have clarified some ma5or mechanisms involved in response to nanoparticles Jne of the important to4icity mechanisms is the 3eneration of reactive o4y3en species (RJS& RJS can dama3e cell membranes, cellular or3anelles and nucleic acids contained in +N= and RN= (@offman et al , %$$;& Throu3h these in7vitro studies, more ecolo3ically relevant to4icity measurements have been developed

1.13 Reactive O7ygen Species (ROS*

=n atom or a 3roup of atoms that have one or more unpaired electrons is a called a radical or a free radical They have a very hi3h reactivity Radicals are essential intermediates in a variety of biochemical reactions, but 0hen these are 3enerated in e4cess and not controlled properly, radicals can dama3e a broad ran3e of macromolecules +ue to their e4tremely hi3h chemical reactivity, they can under3o biolo3ical activities and dama3e cells There are many types of radicals, out of these the radicals 0hich are of most concern in biolo3ical systems are derived from o4y3en and are collectively kno0n as reactive o4y3en species (RJS& J4y3en is susceptible to radical formation because of the presence of t0o unpaired electrons in the outermost cells E4amples of RJS are supero4ide anion ( &, pero4ide ( , hydro4yl radical (J@&, and sin3let o4y3en ( &, an e4cited form of o4y3en RJS are a part of normal aerobic life processes, e 3 in mitochondria, these are formed 0hen o4y3en is reduced alon3 the electron transport chain 6ut RJS can be to4ic if present in abundance like all other radicals They can dama3e macromolecules like lipids, proteins and nucleic acids Their effect on cellular membranes (plasma, mitochondrial and endomembrane systems& has been studied in details (6o0en, %$$"& J4idative stress in terms of RJS 3eneration is used a parameter to 2uantitatively analyse to4icity and ecoto4icity of nanoparticles ?ells

respond to o4idative stress by 3eneratin3 a number of protective responses 0hich can be measured as en8ymatic or 3enetic e4pression responses (Kovochich et al , %$$;& Several in7vitro studies on to4icity of nanoparticles have sho0n 3eneration of RJS, e 3 by Ti (Con3 et al , %$$<& and fullerenes (Sayes et al , %$$A& /n contrary, some authors have also found that nanoparticles, like fullerenes, may protect a3ainst o4idative stress (+aroc8i et al , %$$<E 9an3 et al , !>>>& This obvious contradiction underlines the need for research on nanoparticle7cell interactions .any nanoparticles are photo chemically active and can 3enerate e4ited electrons 0hen e4posed to li3ht, e 3 Ti , *nJ, Si , fullerenes /n presence of o4y3en, these electrons can form supero4ide radicals by direct electron transfer (@offman et al , %$$;& Thus, situations, 0here or3anisms are e4posed to li3ht and nanoparticles simultaneously, are of specific concern for to4icity studies

1.14 $coto7icity

Ecoto4icity studies have been performed for different trophic levels includin3 microor3anisms, plants, invertebrates and vertebrates Test systems have been standardi8ed for some or3anisms and for some e4posure conditions There are protocols approved by the JE?+ (Jr3anisation for Economic ?o7operation and +evelopment& or /SJ (/nternational Jr3ani8ation for Standardi8ation& on ho0 to test the adverse effects of e 3 heavy metals or pesticides to0ards earth0orms, daphnia or 8ebrafish The standardi8ed protocols specify some physical and physiolo3ical conditions (medium composition, a3e of or3anisms, etc & as 0ell as e4posure times (e 3 for acute or chronic to4icity& and 0hich endpoints to measure (3ro0th, fecundity, activity of en8ymes, e4pression of 3enes, etc & 6ut there is a still 0ider ran3e of or3anisms livin3 in nature 0hich re2uire methodolo3ies that are non7standardi8ed to test 0hether a substance has harmful effects on or3anisms or processes affectin3 them in the environment .any studies employ microor3anisms as test or3anisms (mainly bacteria, but also fun3i, proto8oa and al3ae& because they are hi3hly diverse, present in a varied ran3e of habitats and functions&, small (permittin3 miniaturi8ed tests& and 0ith short 3eneration times (permittin3 rapid tests& =lso, they are in immediate contact 0ith li2uids and surfaces

and absorb nutrients and other molecules from their environment directly throu3h their cell 0alls

1.14.1 $coto7icity of C/5 'u erenes

?<$ fullerenes 0ere amon3 the first N'S to be studied for their to4ic effects on environment Co0 concentration of ?<$ ($ A m3-litter& has been found to cause o4idative dama3e and en8yme chan3es in fish (lar3emouth bassE .icropterus salmoides& (Jberdorster, %$$D& Tetrohydrofuran (T@F& 0as used as a solvent in these e4periments, to obtain an a2ueous suspension of colloidal ?<$ a33re3ate referred as n?<$ Cater it 0as sho0n that n?<$ traps T@F from the solution and keeps releasin3 it for lon3 to4icity effects (6rant et al , %$$Aa& /f alternative methods are used for preparin3 n?<$, different to4icity results 0ere found E4periments by Jberdorster et al (%$$<& on the to4icity of n?<$ to +aphnia sho0ed delayed moltin3 and reduced offsprin3 production at % A m3-litter .ortality 0as lo0er than A$B at the ma4imum possible concentration of ?<$ /n presence of :I li3ht inactivate viruses such as bacteriopha3esE to an e4tent more than :I li3ht alone +erived fullerenes e 3 ?<$7N@% inhibited 3ro0th, reduced substrate uptake and resulted in cellular dama3e in % bacterial species (E.coli and Shewanella oneidensis& at a concentration of !$ m3-litter (Tan3 et al , %$$;&

1.14.2 $coto7icity of carbon nanotubes

Sin3le 0alled and double 0alled ?NTs 0ere investi3ated for ecoto4icity to 8ebrafish (Dania rerio& under different salinity conditions (?hen3 et al , %$$;& = si3nificant hatchin3 delay 0as observed in 8ebrafish embryos at concentration 3reater than !%$ m3-litter of S9?NTs +ouble 0alled ?NTs also induced a hatchin3 delay in concentration 3reater than %D$ m3-litter ?arbon black did not affect the hatchin3 Embryonic development 0as not affected by S9?NT up to a concentration of "<$m3-litter @atchin3 delay observed in this study could be because of trace concentration of ?o and Ni catalyst that remained in the solution Iel8eboer and his colle3ues have sho0n that no si3nificant effect of .9?NTs occurs on biodiversity They have ar3ued that the anticipated concentration of .9?TS, as mentioned in the literature is lo0er than the lo0est concentration used in his studies, thereby concludin3 that

community effect are not likely to occure at environment relevent .9?NT loadin3 in a2uatic systems

1.14.3 $coto7icity of 2eta !anopartic es

Silver Nanoparticles are mainly used for antiseptic applications They have 0ell documented bactericidal and cytoto4ic effects Studies have sho0n that nano silver has to4ic effects to0ards or3anisms like E.coli (No0ack et al , %$$;& ?opper nanoparticles are used as antimicrobial a3ents similar to silver nanoparticles /n an e4periment conducted by Kriffit and co70orkers, ?opper to4icity to0ards 8ebrafish (D. rerio& 0as studied (Kriffit et al , %$$;& /t 0as sho0n in this study that ?u nanoparticles 0ere less to4ic than ?u ions E4posure to both formations resulted in similar 3ill in5uries Kold nanoparticles are 0idely used in biomedical ima3in3 and dia3nostic tests :se of 3old particles is assumed to be safe and have not sho0n si3nificant to4icity (Honer et al , %$$;&

Titanium +io4ide (Ti &, *inc J4ide (*nJ& and Silica (Si & nanoparticles are e4tensively in use, e 3 in sunscreen products These nano particles are 0idely produced and applied because of their optical, catalytic, semiconductin3, pie8oelectric and ma3netic properties (No0ack and 6ucheli, %$$;& =n ecoto4icity e4periment 0ith al3ae (Desmodesmus subspicatus& and daphnia (+ ma3na& e4posed to pre7illuminated Ti sho0ed that al3ae 0ere the most sensitive of the t0o (@und7Rinke and Simon %$$<& /n this e4periment, enhanced to4icity induced by pre7 illuminatin3 Ti particles sho0s that the photocatalytic activity of nanoparticles can last very lon3 'hytoto4icity of EN's has been observed for *n and *nJ as inhibition of seed 3ermination and root 3ro0th after % hour e4posure to EN' suspensions in deioni8ed 0ater (Cin and (in3 %$$;& @uman e4posure to nanomaterials may occur throu3h in3estion, inhalation, in5ection and dermal e4posure dependin3 on the source and situation of a person /n3estion e4posure may occur from consumin3 nanomaterials contained in drinkin3 0ater or food /nhalation of nanoparticles at 0orkplace has been reco3ni8ed as a dan3erous e4posure route to 0orkers The small si8e, solubility and lar3e surface area of nanomaterials enable them to interact 0ith different biolo3ical systems The potential to4icity and likelihood of pulmonary deposition increases

0ith reduction in nanomaterial si8e Ti and *nJ used in cosmetic products and sunscreens, lead to direct dermal e4posure /n healthy skin, the epidermis may prevent nanoparticles to mi3rate to dermis @o0ever, dama3ed skin may allo0 nanoparticles to penetrate the dermis and access re3ional lymph nodes (E'= %$!$&

1.1" $nviron.enta 8a9ards and Risks

To develop Nanotechnolo3y in a sustainable 0ay, " R1s, Risk, Response and Re3ulation need to be taken into account (9it, %$$;& The complete risk assessment of nanoparticles re2uires assessin3 the ha8ard that can be caused by nanoparticles and also the e4posure levels that are associated 0ith them Since nanoparticles are still in their development phase, it is premature to attempt their environmental risk assessment ?urrent researches for environmental ha8ard assessment of chemicals basically are findin3 out 0hat are the safe concentrations of nanoparticles that can be e4posed to, 0ithout causin3 adverse effects on environment =lso, nanotechnolo3y can have many positive outcomes to the environment, such as, sustainable ener3y production, environmental remediation and other efficient products These outcomes can over0ei3h the ne3ative impacts, if any, associated 0ith the use of nanoparticles Thus, a complete risk assessment for nanoparticles should be done to find their impact on environment

Conclusions
Nanoparticles are hi3hly mobile and reactive because of their small si8e or hi3h surface area to volume ratio They possess uni2ue properties 0hich are si3nificantly different from the lar3er particles of similar composition These properties have been e4ploited by researchers to desi3n nanoparticles 0ith en3ineered properties 0hich can be used for various applications En3ineered nanomaterials are bein3 used in a 0ide variety of applications includin3 environmental remediation, pollution sensors, photovoltaics, medical ima3in3 and dru3 delivery Nanoparticles are inevitably released in the environment because of their increased usa3e Nanoparticles can be transported to lar3e distances throu3h media such as air, 0ater or soil, and can interact 0ith the media in a variety of 0ays The nanoparticle mobility depends on various physical and chemical factors such as surface chemistry, particle si8e and interaction in media They may stay in suspension as individual particles, a33re3ate, dissolve or react 0ith natural materials, in the environment ?ompared to conventional pollutants, nanoparticles pose ne0 challen3es for researchers :nderstandin3 the behaviour and effects of nanoparticles is important in the conte4t of increasin3 applications of nanoparticles in various fields Si3nificant pro3ress has been made in understandin3 the effect of nanoparticles on the environment and the factors influencin3 their fate and transport, over past decades Luantitative studies have been conducted, 0hich lay out the parameters that have to be considered on a 3lobal scale, to define the properties and subse2uent effects of nanoparticles ?lassical as 0ell as ne0 information has been tried to fit into the modellin3 of fate of nanoparticles and colloids Research is 3oin3 on to improve the characterisation of nanoparticles, so that their subse2uent effects on environment can be predicted There is a need to develop more specific structure7activity relationship for nanoparticles This 0ill help the understandin3 of reactivity of different forms of sin3le nanoparticle (9esterhoff, %$!%& =lso there is a need of parameters that can be studied in laboratory but are more relevant in actual environmental conditions that 3ive an insi3ht of the potential risk associated 0ith the nanoparticles The upcomin3 research re2uires tools to detect and 2uantify nanoparticles in natural 0aters, sediments, soil, 0aste, and se0a3e slud3e 0hich can be used to describe the fate, e4posure and risks associated 0ith the spread of nanoparticles in

environment So far, scientific evidences sho0 that certain nanoparticles have to4ic effects under lab conditions, ho0ever under actual environmental conditions nothin3 much is kno0n about the behaviour of nanoparticles There is a need for research on interaction bet0een nanoparticles and environmental components (0ater, sediments and soil&, and ecoto4icity studies of nanoparticles to understand their environmental effects so that suitable control measures can be dra0n

RE'ERENCES

=vella, . , +e Ilie3er, H H , Errico, . E , Fischer, S , Iacca, ' , and Iolpe, . K (%$$A& 6iode3radable starch-clay nanocomposite films for food packa3in3 applications Food Chemistry >", D<;7D;D 6rant, H , Cecoanet, @ , and 9iesner, . R (%$$Ab& =33re3ation and deposition characteristics of fullerene nanoparticles in a2ueous systems Journal of Nanoparticle Research ;, ADA7AA" 6rant, H , Cecoanet, @ , @ot8e, . , and 9iesner, . (%$$Aa& ?omparison of electrokinetic properties of colloidal fullerenes (n7?7<$& formed usin3 t0o procedures Environmental Science and Technolo y ">, <"D"7<"A! 6uffle, H (%$$<& The key role of environmental colloids-nanoparticles for the sustainability of life Environmental Chemistry ", !AA7!A# ?hen3, H , Flahaut, E , and ?hen3, S @ (%$$;& Effect of carbon nanotubes on developin3 8ebrafish (+aniorerio& embryos Environmental To!icolo y and Chemistry %<, ;$#7;!< ?olvin, I C , (%$$"& The potential environmental impact of en3ineered nanomaterials Nature "iotechnolo y, %!, !!<<7!!;$ Ail +/R/ and +arak :/E/ & 2008* $omposite 'anoparticles 4ake ,im at $ancer. ACS Nano/ 2 &11* 2200%220=/ Kimbert, C H , @amon, R E , ?asey, ' S , and 9orsfold, ' H (%$$;& 'artitionin3 and stability of en3ineered *nJ nanoparticles in soil suspensions usin3 flo0 field7flo0 fractionation Environmental Chemistry D, #7!$ Kriffitt, R H , 9eil, R , @yndman, K = , +enslo0, N + , 'o0ers, K , Taylor, + , and 6arber, + S (%$$;& E4posure to copper nanoparticles causes 3ill

in5ury and acute lethality in 8ebrafish (+anio rerio& Environmental Science and Technolo y. D!, #!;#7#!#< @ansen, S F , .ichelson, E S , Kamper, = , 6orlin3, ' , Stuer7Cauridsen, F , 6aun, = (%$$#& ?ate3ori8ation frame0ork to aid e4posure assessment of nanomaterials in consumer products Ecoto!icolo y !;, D"#FDD; @artland, = , Cead, H R , Slaveykova, I / , J1?arroll, + N Ialsami7Hones, E (%$!"& The Environmental Si3nificance of Natural Nanoparticles Nature Education #nowled e D(#&,; @und7Rinke, K , and Simon, . (%$$<& Ecoto4ic effect of photocatalytic active nanoparticles TiJ% on al3ae and daphnids Environmental Science and $ollution Research !", %%A7%"% @yun3, @ , Fortner, H + , @u3hes, H 6 , and Kim, H @ (%$$;& Natural or3anic matter stabili8es carbon nanotubes in the a2ueous phase Environmental Science and Technolo y D!, !;>7!#D Honer, Erik H , @artnik, T , =mundsen ? E (%$$;& Environmental fate and ecoto4icity of en3ineered nanoparticles Norwe ian $ollution Control %uthority. Report No T=7%"$D-%$$; Hones, . N , and 6ryan, N + (!>>#& ?olloidal properties of humic substances %dvances in Colloid &nterface Sciences ;#, !7D# Klaine, S H , =lvare8, ' H H , 6atley, K E , Fernandes, T E , @andy, R + , Cyon, + ) , .ahendra, S , .cCau3hlin, . H , and Cead , H R (%$$#& Nanoparticles in the Environment, 6ehaviour, Fate, 6ioavailability and Effects Environmental To!icolo y and Chemistry, %; (>&, !#%A7 !#A! Cecoanet, @ F , 6ottero H ) , and 9iesner, . R , (%$$D& Caboratory assessment of the mobility of nanomaterials in porous media Environmental Science and Technolo y "#, A!<D7A!<> Cin, + , and (in3, 6 (%$$;& 'hytoto4icity of nanoparticles, /nhibition of seed 3ermination and root 3ro0th Environmental $ollution !A$, %D"7%A$ Cuoma, S N (%$$#& Silver Nanotechnolo3ies and the environment 'oodrow 'ilson &nternational Center for Scholars .ichalet, ( , 'inaud, F F , 6entolila, C = , Tsay, H . , +oose, S , Ci, H H , Sundaresan, K , 9u = . , Kambhir, S S and 9eiss, S , %$$A Luantum dots for live cells, in vivo ima3in3, and dia3nostics Science "$;(A;$>&, A"#7 ADD

No0ack, 6 , and 6ucheli, T + (%$$;& Jccurrence, behaviour and effects of nanoparticles in the environment Environmental $ollution( !A$, A7%% JberdOrster, E (%$$D& .anufactured nanomaterials (Fullerenes, ?<$& induce o4idative stress in the brain of 5uvenile lar3emouth bass Environmental )ealth $erspectives !!%, !$A#7!$<% Jberdorster, E , *hu, S L , 6lickley, T . , .c?lellan7Kreen, ' , and @aasch, . C (%$$<& Ecoto4icolo3y of carbon7based en3ineered nanoparticles, Effects of fullerene (?7<$& on a2uatic or3anisms Carbon DD, !!!%7!!%$ J1.elia, ? R (!>;%& ?oa3ulation and flocculation /n 'hysicochemical 'rocesses for 9ater Luality ?ontrol Ed 9 H 9eber 5r pp <!7!$> 'iley &nterscience, Ne0 )ork Rose, H , Thill, = , and 6rant, H (%$$;& .ethods for structural and chemical characteri8ation of nanomaterials /n Environmental Nanotechnolo3y =pplications and /mpacts of Nanomaterials Eds . R 9iesner and H ) 6ottero pp !$A7!AD *c+raw )ill, Ne0 )ork Ryan, H N , and Elimelech, . (!>><& ?olloid mobili8ation and transport in 3round0ater Colloid Surface = !$;, !7A< Tan3, ) H H , =shcroft, H . , ?hen, + , .in, K 9 , Kim, ? @ , .urkhe5ee, 6 , Carabell, ? , Keaslin3, H + , and ?hen, F L F (%$$;& ?har3e7associated effects of fullerene derivatives on microbial structural inte3rity and central metabolism Nano ,etters ;, ;AD7;<$ Tran, ? C , +onaldson, K , Stones, I , Fernande8, T , Ford, = , ?hristofi, N (%$$A& = scopin3 study to identify ha8ard data needs for addressin3 the risks presented by nanoparticles and nanotubes Edinbur3h, Scotland, /nstitute of Jccupational .edicine Iel8eboer, / , Kpryianchyk, + , 'eeters, ET@. , Koelenans, = = (%$!!& ?ommunity effects of carbon nanotubes in a2uatic sediments, Environment &ntervation ";, !!%<7!!"$ 9esterhoff, ' , and No0ack, 6 (%$!%& Searchin3 for 3lobal +escriptors of en3ineered nanomaterial fate and transport in the environment %ccounts of chemical Research 9iesner, . R , Co0ry, K I , =lvare8, ' , +ionysiou, + , and 6is0as, ' , (%$$<& =ssessin3 the risks of manufactured nanomaterials Environmental Science and Technolo y( D$, D""<7D"DA

9it, ?ynthia de, (%$$>& Ne0 nanomaterials environmental risks and possibilities Summary of a Symposium at Royal Swedish %cademy of Sciences

Web References E'= ?ontrol of Nanoscale .aterials under the To4ic Substances ?ontrol =ct (%$!$& Phttp,--000 epa 3ov-oppt-nano-Q (accessed on $A $> %$!"& E'= Nanotechnolo3y for site Remediation Fact Sheet (%$$#a& Phttp,--000 clu7in or3-do0nload-remed-AD%7f7$#7$$> pdfQ (accessed on $% $> %$!"& E'= Senior 'olicy ?ouncil Nanotechnolo3y 9hite 'aper (%$$;& Phttp,--000 epa 3ov-osa-pdfs-nanotech-epa7nanotechnolo3y70hitepaper7 $%$; pdfQ (accessed on $A $> %$!"& 9atlin3ton, K (%$$A& Emer3in3 Nanotechnolo3ies for Site Remediation and 9aste0ater Treatment Phttp,--000 clu7 in or3-do0nload-studentpapers-KR9atlin3tonR Nanotech pdfQ (accessed on $A $> %$!"& 9oodro0 9ilson /nternational ?enter of Scholar (99/?& (%$!"& Phttp,--000 nanotecpro5ect or3-inventories-consumer-Q (accessed $% $> %$!"&

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Jr3anic ?ompounds (J?& (%$!"& Phttp,--000 landfood ubc ca-soil%$$-components-or3anicRcompounds ht mlS%!!Q (accessed on %" $> %$!"& @umic Substances (@S& (accessed on %" $> %$!"& (%$!"& Phttp,--000 humicsubstances or3Q