Microplastics Degradation and Characterization

399 Pages·2022·21.05 MB·English

by  Jacopo La Nasa

Microplastics
Degradation and
Characterization
Edited by
Jacopo La Nasa
Printed Edition of the Special Issue Published in Polymers
www.mdpi.com/journal/polymers
Microplastics Degradation and
Characterization
Microplastics Degradation and
Characterization
Editor
Jacopo La Nasa
MDPI‚Basel‚Beijing‚Wuhan‚Barcelona‚Belgrade‚Manchester‚Tokyo‚Cluj‚Tianjin
Editor
JacopoLaNasa
DepartmentofChemistryand
IndustrialChemistry
UniversityofPisa
Pisa
Italy
EditorialOffice
MDPI
St. Alban-Anlage66
4052Basel,Switzerland
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Contents
Valter Castelvetro, Andrea Corti, Jacopo La Nasa, Francesca Modugno, Alessio Ceccarini
andStefaniaGiannarellietal.
PolymerIdentificationandSpecificAnalysis(PISA)ofMicroplasticTotalMassinSedimentsof
the ProtectedMarineAreaoftheMeloriaShoals
Reprintedfrom: Polymers2021,13,796,doi:10.3390/polym13050796 . . . . . . . . . . . . . . . . . 1
Sabiqah Tuan Anuar, Raad Shaher Altarawnah, Ahmad Ammarluddin Mohd Ali, Bai Qin
Lee,WanMohdAfiqWanMohdKhalikandKuMohdKalkausarKuYusofetal.
Utilizing Pyrolysis–Gas Chromatography/Mass Spectrometry for Monitoring and Analytical
CharacterizationofMicroplasticsinPolychaeteWorms
Reprintedfrom: Polymers2022,14,3054,doi:10.3390/polym14153054 . . . . . . . . . . . . . . . . 19
Solange Magalha˜es, Lu´ıs Alves, Anabela Romano, Bruno Medronho and Maria da Grac¸a
Rasteiro
ExtractionandCharacterizationofMicroplasticsfromPortugueseIndustrialEffluents
Reprintedfrom: Polymers2022,14,2902,doi:10.3390/polym14142902 . . . . . . . . . . . . . . . . 33
Diego David Pinzon-Moreno, Isabel Rosali Maurate-Fernandez, Yury Flores-Valdeon,
AntonyAlexanderNeciosup-PuicanandMarı´aVero´nicaCarranza-Oropeza
Degradation of Hydrogels Based on Potassium and Sodium Polyacrylate by Ionic Interaction
andItsInfluenceonWater
Reprintedfrom: Polymers2022,14,2656,doi:10.3390/polym14132656 . . . . . . . . . . . . . . . . 45
LalitsudaPhutthimethakulandNutaSupakata
PartialReplacementofMunicipalIncineratedBottomAshandPETPelletsasFineAggregatein
CementMortars
Reprintedfrom: Polymers2022,14,2597,doi:10.3390/polym14132597 . . . . . . . . . . . . . . . . 61
NguyenThaoNguyen,NguyenThiThanhNhon,HoTruongNamHai,NguyenDoanThien
ChiandToThiHien
Characteristics of Microplastics and Their Affiliated PAHs in Surface Water in Ho Chi Minh
City,Vietnam
Reprintedfrom: Polymers2022,14,2450,doi:10.3390/polym14122450 . . . . . . . . . . . . . . . . 79
Ilaria Savino, Claudia Campanale, Pasquale Trotti, Carmine Massarelli, Giuseppe Corriero
andVitoFeliceUricchio
Effects and Impacts of Different Oxidative Digestion Treatments on Virgin and Aged
MicroplasticParticles
Reprintedfrom: Polymers2022,14,1958,doi:10.3390/polym14101958 . . . . . . . . . . . . . . . . 99
Ba´rbara Abaroa-Pe´rez, Sara Ortiz-Montosa, Jose´ Joaqu´ın Herna´ndez-Brito and Daura
Vega-Moreno
Yellowing, Weathering and Degradation of Marine Pellets and Their Influence on the
AdsorptionofChemicalPollutants
Reprintedfrom: Polymers2022,14,1305,doi:10.3390/polym14071305 . . . . . . . . . . . . . . . . 121
MartinaMilolozˇa,KristinaBule,ViktorijaPrevaric´,MatijaCvetnic´,SˇimeUkic´andTomislav
Bolancˇaetal.
Assessment of the Influence of Size and Concentration on the Ecotoxicity of Microplastics to
MicroalgaeScenedesmussp.,BacteriumPseudomonasputidaandYeastSaccharomycescerevisiae
Reprintedfrom: Polymers2022,14,1246,doi:10.3390/polym14061246 . . . . . . . . . . . . . . . . 133
v
Claudia Cella, Rita La Spina, Dora Mehn, Francesco Fumagalli, Giacomo Ceccone and
AndreaValsesiaetal.
DetectingMicro-andNanoplasticsReleasedfromFoodPackaging: ChallengesandAnalytical
Strategies
Reprintedfrom: Polymers2022,14,1238,doi:10.3390/polym14061238 . . . . . . . . . . . . . . . . 153
Cristina De Monte, Marina Locritani, Silvia Merlino, Lucia Ricci, Agnese Pistolesi and
SimonaBronco
AnInSituExperimenttoEvaluatetheAgingandDegradationPhenomenaInducedbyMarine
EnvironmentConditionsonCommercialPlasticGranules
Reprintedfrom: Polymers2022,14,1111,doi:10.3390/polym14061111 . . . . . . . . . . . . . . . . 167
Chun-TingLin,Ming-ChihChiuandMei-HwaKuo
AMini-ReviewofStrategiesforQuantifyingAnthropogenicActivitiesinMicroplasticStudies
inAquaticEnvironments
Reprintedfrom: Polymers2022,14,198,doi:10.3390/polym14010198 . . . . . . . . . . . . . . . . . 193
MehmetMuratMonkulandHakkıO.O¨zhan
MicroplasticContaminationinSoils: AReviewfromGeotechnicalEngineeringView
Reprintedfrom: Polymers2021,13,4129,doi:10.3390/polym13234129 . . . . . . . . . . . . . . . . 211
FranjaProsenc,PiaLeban,UrsˇkaSˇuntaandMojcaBavconKralj
ExtractionandIdentificationofaWideRangeofMicroplasticPolymersinSoilandCompost
Reprintedfrom: Polymers2021,13,4069,doi:10.3390/polym13234069 . . . . . . . . . . . . . . . . 235
SolaChoi,MiyeonKwon,Myung-JaParkandJuheaKim
AnalysisofMicroplasticsReleasedfromPlainWovenClassifiedbyYarnTypesduringWashing
andDrying
Reprintedfrom: Polymers2021,13,2988,doi:10.3390/polym13172988 . . . . . . . . . . . . . . . . 251
GretaBiale,JacopoLaNasa,MarcoMattonai,AndreaCorti,VirginiaVinciguerraandValter
Castelvetroetal.
A Systematic Study on the Degradation Products Generated from Artificially Aged
Microplastics
Reprintedfrom: Polymers2021,13,1997,doi:10.3390/polym13121997 . . . . . . . . . . . . . . . . 263
Valeria Caponetti, Alexandra Mavridi-Printezi, Matteo Cingolani, Enrico Rampazzo,
DamianoGenoveseandLucaProdietal.
ASelectiveRatiometricFluorescentProbeforNo-WashDetectionofPVCMicroplastic
Reprintedfrom: Polymers2021,13,1588,doi:10.3390/polym13101588 . . . . . . . . . . . . . . . . 287
Aranza Denisse Vital-Grappin, Maria Camila Ariza-Tarazona, Valeria Montserrat
Luna-Herna´ndez, Juan Francisco Villarreal-Chiu, Juan Manuel Herna´ndez-Lo´pez and
CristinaSiligardietal.
The Role of the Reactive Species Involved in the Photocatalytic Degradation of HDPE
MicroplasticsUsingC,N-TiO Powders
2
Reprintedfrom: Polymers2021,13,999,doi:10.3390/polym13070999 . . . . . . . . . . . . . . . . . 303
LukasMiksch,LarsGutowandReinhardSaborowski
pH-StatTitration: ARapidAssayforEnzymaticDegradabilityofBio-BasedPolymers
Reprintedfrom: Polymers2021,13,860,doi:10.3390/polym13060860 . . . . . . . . . . . . . . . . . 321
vi
Benjamin O. Asamoah, Pauliina Salmi, Jukka Ra¨ty, Kalle Ryymin, Julia Talvitie and Anna
K.Karjalainenetal.
Optical Monitoring of Microplastics Filtrated from Wastewater Sludge and Suspended in
Ethanol
Reprintedfrom: Polymers2021,13,871,doi:10.3390/polym13060871 . . . . . . . . . . . . . . . . . 335
Benjamin O. Asamoah, Emilia Uurasja¨rvi, Jukka Ra¨ty, Arto Koistinen, Matthieu Roussey
andKai-ErikPeiponen
Towards the Development of Portable and In Situ Optical Devices for Detection of Micro-and
NanoplasticsinWater: AReviewontheCurrentStatus
Reprintedfrom: Polymers2021,13,730,doi:10.3390/polym13050730 . . . . . . . . . . . . . . . . . 349
HongxiaLi,JianqunYang,FengTian,XingjiLiandShangliDong
StudyontheMicrostructureofPolyetherEtherKetoneFilmsIrradiatedwith170keVProtons
byGrazingIncidenceSmallAngleX-rayScattering(GISAXS)Technology
Reprintedfrom: Polymers2020,12,2717,doi:10.3390/polym12112717 . . . . . . . . . . . . . . . . 377
vii
polymers
Article
Polymer Identification and Specific Analysis (PISA) of
Microplastic Total Mass in Sediments of the Protected
Marine Area of the Meloria Shoals
ValterCastelvetro1,2,* ,AndreaCorti1,2,JacopoLaNasa1 ,FrancescaModugno1,2,AlessioCeccarini1,
StefaniaGiannarelli1 ,VirginiaVinciguerra1,2andMonicaBertoldo3,4
1 DepartmentofChemistryandIndustrialChemistry,UniversityofPisa,56124Pisa,Italy;
[email protected](A.C.);[email protected](J.L.N.);[email protected](F.M.);
[email protected](A.C.);[email protected](S.G.);[email protected](V.V.)
2 CISUP—CenterfortheIntegrationofScientificInstrumentsoftheUniversityofPisa,UniversityofPisa,
56124Pisa,Italy
3 DepartmentofChemical,PharmaceuticalandAgriculturalSciences,UniversityofFerrara,viaL.Borsari,
45121Ferrara,Italy;[email protected]
4 InstituteofOrganicSynthesisandPhotoreactivity,NationalResearchCouncilofItaly(ISOF-CNR),
viaP.Gobetti101,40129Bologna,Italy
* Correspondence:[email protected];Tel.:[phone]
Abstract:Microplastics(MPs)quantificationinbenthicmarinesedimentsistypicallyperformedby
time-consumingandmoderatelyaccuratemechanicalseparationandmicroscopydetection.Inthis
paper,wedescribetheresultsofourinnovativePolymerIdentificationandSpecificAnalysis(PISA)
Citation: Castelvetro,V.;Corti,A.; ofmicroplastictotalmass,previouslytestedoneitherlesscomplexsandybeachsedimentorless
LaNasa,J.;Modugno,F.;Ceccarini, demanding(becauseofthehighMPscontent)wastewatertreatmentplantsludges,appliedtothe
A.;Giannarelli,S.;Vinciguerra,V.; analysisofbenthicsedimentsfromasublittoralareanorth-westofLeghorn(Tuscany,Italy).Samples
Bertoldo,M.PolymerIdentification
werecollectedfromtwoshallowsitescharacterizedbycoarsedebrisinamixedseabedofPosidonia
andSpecificAnalysis(PISA)of
oceanica,andbyaveryfinesilty-organogenicsediment,respectively. Aftersievingat<2mmthe
MicroplasticTotalMassinSediments
sedimentwassequentiallyextractedwithselectiveorganicsolventsandthetwopolymerclasses
oftheProtectedMarineAreaofthe
polystyrene(PS)andpolyolefins(PEandPP)werequantifiedbypyrolysis-gaschromatography-mass
MeloriaShoals.Polymers2021,13,
spectrometry (Pyr-GC/MS). A contamination in the 8–65 ppm range by PS could be accurately
796. https://doi.org/10.3390/
detected.Acidhydrolysisontheextractedresiduetoachievetotaldepolymerizationofallnatural
polym13050796
andsyntheticpolyamides,taggingofallaminatedspeciesinthehydrolysatewithafluorophore,
AcademicEditor:VictorTcherdyntsev andreversed-phasehighperformanceliquidchromatography(HPLC)(RP-HPLC)analysis,allowed
thequantificationwithinthe137–1523ppmrangeoftheindividualmassofcontaminatingnylon6
Received:7February2021 andnylon6,6,basedonthedetectedamountsoftherespectivemonomericamines6-aminohexanoic
Accepted:2March2021 acid(AHA)andhexamethylenediamine(HMDA).Finally,alkalinehydrolysisoftheresiduefrom
Published:5March2021
acidhydrolysisfollowedbyRP-HPLCanalysisofthepurifiedhydrolysateshowedcontaminationby
polyethyleneterephthalate(PET)inthe12.1–2.7ppmrange,basedonthecontentofitscomonomer,
Publisher’sNote:MDPIstaysneutral
terephthalicacid.
withregardtojurisdictionalclaimsin
publishedmapsandinstitutionalaffil-
Keywords:microplastics;marinesediment;pet;nylon6;nylon6,6;reversed-phaseHPLC;polyolefin;
iations.
polystyrene;Pyr-GC/MS;polymerdegradation
Copyright: © 2021 by the authors. 1. Introduction
Licensee MDPI, Basel, Switzerland.
Plasticmicroparticles,commonlyreferredtoasmicroplastics(MPs),eitherderiving
This article is an open access article
fromtheenvironmentaldegradationoflargerplasticwasteitems[1–3]ordirectlyreleased
distributed under the terms and
asprimarymicroparticles(microbeads,textilemicrofibers)inwastewaters,areaclassof
conditionsoftheCreativeCommons
pollutantsdetectedinvirtuallyallnaturalenvironments,fromoceanstoinlandwaters[4],
Attribution(CCBY)license(https://
soils and even as airborne material [5], reaching such remote areas as the Arctic and
creativecommons.org/licenses/by/
4.0/). Antarctica [6,7]. The ubiquitous presence of MPs, and likely so also of their ultimate
1
Polymers2021,13,796
products of further degradation into sub-micrometer sized particles (nanoplastics) [8],
alongwithincipientevidenceoftheiradverseinteractionwithlivingorganisms[9],has
stimulatedincreasingresearcheffortsaimedatunderstandingtheirtransport,distribution
andfate[10–12]. Duetotheirsmallsizemicroplasticcanbeingestedbyvariousorganisms
atalltrophiclevels,andincreasingscientificevidencehighlightsthepossibilityoftheir
transferintoanimaltissueandupthefoodchainreachinghumans[13,14].
Themostcommonsyntheticpolymersinplasticwastearepolyolefins(polypropy-
lene, PP, high density polyethylene, HDPE, and low-density polyethylene, LDPE) and
polystyrene(PS),widelyusedinpackagingandsingle-usedisposableitemssuchastable-
ware;polyester(mainlypolyethyleneterephthalate,PET,usedforbeveragebottles,packag-
ingandasstapletextilefiber)andpolyamides(oftenreferredtoaccordingtothetradename
nylons)representanadditionalsignificantfractionofMPspollution. Inthecaseofpoly-
olefins,theenvironmentaldegradationprocessesaremainlyascribedtophoto-oxidation,
resultinginoxygenpickupduetofreeradicalreactionswithcascadeeffectseventuallylead-
ingtopolymerchainfragmentationandinsertionofoxidizedfunctionalgroups(carbonyls,
carboxyl,hydroxyl,etc.)[15]. Suchchemicaltransformationsbearseveralconsequences:
(i)theinitiallyhighmolecularweightisreducedandthepolymericmaterialbecomesmore
brittle, promoting progressive fragmentation into increasingly smaller particles; (ii) its
densityandhydrophilicityincreasealongwithsurfacepolarityandreactivity,enhancing
adsorption/absorptionoflowmolecularweightorganic(includingtoxicpolycyclicaro-
matichydrocarbons,PAHs,andpolychlorinatedbiphenyls,PCBs)andinorganic(heavy
metals)environmentalpollutants;(iii)increasedwettabilityandspecificsurfaceareafa-
cilitatebiofoulingandadhesioninorganicparticulate,alloftheabovepromotingsinking
downthewatercolumnanddepositioninbothshoreandbenthicsediments[16–19]. Ithas
beenestimatedthatlessthan1%ofthe5–12milliontonsperyearofplasticsenteringthe
oceansstaysafloatforalongtime,theremainingfractionreachingtheseabedeitherina
veryshorttime(thisisthecaseoflargeritemsofhigherdensityplasticssuchase.g.,PETor
low-densitypolymerswithinorganicfillers)oroverlongerperiodsregardlessoftheinitial
densitybecauseoftheabovementioneddegradationandfoulingphenomena[12,20,21].
Here we report the results of the application of our recently developed analytical
protocol to the quantitative determination of the total mass content of a well-defined
set of microplastics [22], hereafter Polymer Identification and Specific Analysis (PISA),
in benthic marine sediments. The PISA protocol provides accurate quantitative (total
massofthecontaminatingMPsinthesedimentsample,withseparatequantificationfor
eachpolymertype,asspecifiedbelow)andqualitative(typeofpolymer)informationwith
sensitivitiesordersofmagnitudehigherthanthoseattainablewiththegeneralmethodology
mostcommonlyadoptedsofarbyresearchersworldwide. Themethodsdescribedinthe
literature,basedonMPsseparationfromthesedimentbyflotationinahighdensitysaline
solution(NaCl,NaI,Natungstate,etc.) followedbyquantificationandcharacterization
typicallybymeansofopticalmicroscopyandmicro-spectroscopytechniques[23],may
sufferfrominaccuracyduetotheunderestimationcausedbythemisseddetectionofMPs
belowthemeshsizeofthefilteringdevice,andtotheoverestimationcausedbyresidual
biogenicandinorganiccontaminatingmaterial. Inparticular, thePISAprotocolallows
quantification of the total mass of MPs, regardless of their size and morphology, that
areconstitutedbythefollowingpolymers: polyolefins,PS,PET,andthetwopolyamides
nylon6(polycaprolactame,thehomopolymerofAHA)andnylon6,6(copolymerofHMDA,
withadipicacid)[24]. Thesearealsothemaincommoditypolymersand,notincidentally,
arealsoconsideredtobethemainmacro-andmicroplasticmarinepollutants.
Although techniques similar to those comprised in the PISA protocol have been
described,theydonotincludethecompletesetofrelevantpolymers;inparticular,pressur-
izedsolventextraction[25]isquiteeffectiveforpolyolefinsandotherpolymerssolublein
commonsolvents(mainlyPSandothervinylpolymers)butmissesPETandpolyamides
thatarethemostabundantmicroplasticsfromsynthetictextilefibers,whileapreviously
describeddepolymerizationofPETfollowedbyhighperformanceliquidchromatography
2
Polymers2021,13,796
(HPLC)coupledwithmassspectrometry[26]doesnotincludepolyamides. Ontheother
hand,athermoanalyticalmethodbasedontheaccuratequantificationofthetotalcarbon
contentfromsyntheticpolymersrecentlyproposedbyJ.Linetal.[27],besideslosingthe
informationonsizeandshapeasinthePISAprotocol,doesnotallowspecificationofthe
typeofpolymericmaterialsinthecontaminatingMPsandonlyprovidesanestimation
ofthetotalamountofmicroplasticsduetothedifferentfractionalcarboncontentineach
polymertype.
Thebenthicsedimentsamplesanalyzedinthepresentworkwerecollectedintwo
close locations of the sublittoral southern Ligurian Sea close to the harbor of Leghorn
andtheestuaryoftheArnoriver,Italy,andinparticularwithintheshoalsoftheMeloria
protectedmarineareaandinnearbyshallowcoastalwaters,respectively. Thesediments
weresievedat2mmmeshandthensubmittedtoasequenceoffractionalsolventextrac-
tionswithrefluxingdichloromethane(DCM)andxylene(Xy)asselectivesolventsforPS
andpolyolefins,respectively[28],followedbysequentialhydrolyticdepolymerizationof
polyamides,underacidicconditions,andofPET,underalkalineconditions. Althoughthe
extractedpolyolefinsandPSarequantifiedbygravimetryandpyrolysis-GC/MS,thetotal
contentofnylon6,nylon6,6,andPETarecalculatedfromthequantitativeanalysis,by
reversed-phaseHPLC,oftheirrespectivemonomers: thetwoaminesAHAandHMDA
aftertaggingwithafluorophore[29],andterephthalicacid(TPA)[30]. Differentlyfromthe
previouslyreportedexamplesinwhichthisprocedure(orpartofit)hadbeentestedon
lesscomplexsandybeachsedimentorlessdemanding(becauseofthehighMPscontent)
wastewatertreatmentplantsludges,thisisthefirstreportonthePISAprocedureforthe
detectionandquantificationofMPsinbenthicsediments.
2. MaterialsandMethods
2.1. SedimentSampling
Benthic(bottom)marinesedimentsampleswerecollectedinfoursitesofrelatively
shallowwatersofthecontinentalshelfintheLigurianSeaalongthenortherncoastline
of Tuscany, Italy (Table 1). The sampling was performed on 3 July 2018, using a single
corer10cmindiameter. Aftercollection,thetop~5cmofthesedimentwasplacedinglass
flaskswithmetallidandthenair-driedinalaminarflowhoodinthelabandstoredin
◦
afridgeat2 C.Thesubsequentanalyseswereperformedinsecondhalfof2020. Care
wastakenastoavoidcontaminationfromairborneandotherenvironmentalMPs;forthis
purpose,allglasswarewasrinsedwiththegivensolvent(previouslyfilteredon0.45μm
poresizemembrane)priortouse; allopensurfacesofsolutionsandsolidsamplesand
extractswerekeptcoveredwithaluminumfoilsthroughoutthevariousmanipulations
exceptduringtheactualoperationsandtransfer;personalprotectiveequipmentincluded
cottonprotectivecoats.
Table1.Sampleacronymsandrelevantsamplingsitescoordinatesanddepth.
Depth
Sample Acronym Geolocalization
(m)
◦ (cid:3)
43 3250.0”N 43.547219lat.
Meloria1 MEL1 ◦ (cid:3) 3
10 1308.2”E 10.218944lon.
◦ (cid:3)
43 331,02”N 43.5502778lat.
Meloria2 MEL2 ◦ (cid:3) 4
10 134,03”E 10.2177778lon.
◦ (cid:3)
43 355,21”N 43.5847778lat.
Calambrone1 CAL1 ◦ (cid:3) 20
10 172,34”E 10.2839722lon.
◦ (cid:3)
43 369,67”N 43.6026944lat.
Tirrenia-Calambrone2 CAL2 ◦ (cid:3) 17
10 167,80”E 10.2688333lon.
3