Study of Long Range Transported Pollutants in Arctic Soil

134 Pages·2017·18.49 MB·English

by  Carolin Elisabeth Huber

Study of Long Range Transported
Pollutants in Arctic Soil
Carolin Elisabeth Huber
Environmental Toxicology and Chemistry
Submission date: May 2017
Supervisor: Øyvind Mikkelsen, IKJ
Co-supervisor: Eiliv Steinnes, IBI
Norwegian University of Science and Technology
Department of Chemistry

i
Preface
ThisthesiswascarriedoutintheEnvironmentalChemistryandToxicology(ENVITOX)
programfromtheautumnsemester2015untilthespringsemester2017. Fieldwork
andsamplingwasperformedinJuly2016inLongyearbyenandNyÅlesund. Thefield
workwasfundedbyForskingrådet. TheprojectcanbefoundattheRISdatabasewith
thenumber10425.
TheanalysisofbackgroundsoilsamplesfromSvalbardhasalsobeenperformedbytwo
otherNTNUstudents,KatarinaHalbach(2016)andMaritElisabethFors(2014). While
those previous works focused mainly on elemental analysis, this work aims to point
outoccurringcorrelationsondifferentsamplingsitesandalsoworksontheanalysisof
PolychlorinatedBiphenyls.
Trondheim,2017-05-10
signature
CarolinElisabethHuber
ii
Acknowledgment
Iwouldliketothankthefollowingpersonsfortheirgreathelpduringthetimeofac-
complishingthiswork:
MymainsupervisorØyvindMikkelsen,forguidancethroughouttheprojectandhelpful
feedbackontheresultsandforsupportduringsamplinginSvalbard. RudolfSchmidt
fortheguidancethroughtheGC-MSpart. IalsothankSyverinLierhagenfortheICP-
MSanalysis.
DorienDunnebierforthehelpfulsuggestionsduringthelastweeksofwriting.
C.H.
iii
Abstract
Inthismasterthesis,levelsofPolychlorinatedBiphenyls(PCBs),totalorganiccarbon
(TOC)andpotentiallylongrangetransportedinorganicelements(Cd, HgandPb)in
surfacesoilandvegetationhavebeenstudiedforsamplesfromSvalbard(Norwegian
Arctic). 74 soil and 35 vegetation samples were taken at six different sampling sites
whichprovidebackgroundlevels.
FormeasurementofPCBsinsoilamethodhadbeendevelopedfortheuseofacceler-
atedsolventextractionandgaschromatographycoupledwithtandemmassspectrom-
etry.Differentcleanupmethodshavebeentested.
ResultsmaintainedfromacertifiedlaboratoryshowedabundanceofPCB52insoiland
vegetationsampleswithameanof3,0±1,2ng/ginsoiland5,9±2,5ng/ginvegetation.
PCB180wasfoundforsamplesitesinLeinstranda(NyÅlesund). PCB28wasfoundin
twovegetationsamples.Othermeasuredcongeners(101,118,138,153)wereunderthe
limitofquantification(LOQ=1ng/g).
AmeanconcentrationofHgof155±83ng/ginsoiland97,4±32,8ng/ginvegetation
wasobtained,withsignificanthigherresultsforsamplesitesclosetoLongyearbyen.Hg
significantlycorrelateswithSandClinsoil.MeasuredPblevelsinsoilshowameanof
31,5±10,6µg/gandseemtoresultfromthesoilparentmaterial.Cdlevels(mean0,489
± 0,295 µg/g in soil) were high correlated with TOC. Higher levels and variation was
foundforCdinvegetationsamples(0,595±0,371µg/g).
iv
Acronyms
ACP Arcticcontaminationpotential
AMAP Arcticmonitoringandassessmentprogram
ASE Acceleratedsolventextraction
CBz Chlorobenzene
CLTRAP Conventiononlongrangetransboundarypollution
DDE Dichlorodiphenyldichlorethene
DDT Dichlorodiphenyltrichlorethane
DL/NDL Dioxinlike/non-dioxinelike
FA Factoranalysis
GC Gaschromatography
Globo-POP Globaldistributionmodelofpersistentorganicpollutants
HCB Hexachlorobenzene
HCH Hexachlorohexane
ISTD Internalstandard
RSTD Recoverystandard
SIM Singleionmonitoring
SOM Soilorganicmatter
TOC Totalorganiccarbon
K Partitioncoefficientbetweenairandwater
AW
K Partitioncoefficientbetweenoctanolandair
OA
K Partitioncoefficientbetweensolid(organic)phaseandwater
OC
K Partitioncoefficientbetweenoctanolandwater
OW
K Partitioncoefficientbetweensoilorganicmatterandair
SA
LOI Lossonignition
LRAT Longrangeatmospherictransport
MS Massspectrometry
v
MS/MS Tandemmassspectrometry
OC Organochlorines
PAH PolyaromaticHydrocarbons
PBDE Polybrominateddipheylether
PCB PolychlorinatedBiphenyls
PCA Principalcomponentanalysis
PCDD Polychlorinateddipenzo-p-dioxin
PCDF Polychlorinateddipenzo-p-furan
PFOS Perfluorooctanesulforicacid
POP Persistentorganicpollutant
vi
List of Tables
2.1 HistoricalfactsaboutPCBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2 LevelsofPCBsintheArctic . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.1 TableofpreviousstudiesonPCBsinSvalbard . . . . . . . . . . . . . . . . . 25
4.1 SpecificationoftheICP-MSinstrumentationandextraction. . . . . . . . . 36
4.2 MethodvalidationforICP-MS . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.3 StandardsolutionsI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.4 StandardsolutionsII . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.5 RetentiontimesI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4.6 RetentiontimesII . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.7 Massnumbersofrecoverystandard . . . . . . . . . . . . . . . . . . . . . . . 47
4.8 ConditionsforASE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.9 SpecificationsforMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.10 SpecificationsforGC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.11 MassnumbersforSIM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
4.12 AnalysissegmentsforSIM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.13 SpecificationsforMS/MSmode . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.14 BlanklevelsofPCBanalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.15 Resultsofreferencematerialanalysis . . . . . . . . . . . . . . . . . . . . . . 58
4.16 Responsefactorandrecoveryfromspikedsamples . . . . . . . . . . . . . . 59
4.17 Responsefactorandrecoveryfromcalibrationsolution . . . . . . . . . . . 59
4.18 SpecificationoftheHYSPLITcalculations . . . . . . . . . . . . . . . . . . . 62
5.1 DescriptivestatisticsforPCBanalysis . . . . . . . . . . . . . . . . . . . . . . 70
5.2 TotalorganiccarbonforsurfacesoilsinSvalbard . . . . . . . . . . . . . . . 73
5.3 TableofloadingsforvariablesinFA(A) . . . . . . . . . . . . . . . . . . . . . 79
6.1 LODlevelsforPCBanalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6.2 Comparisonwithpreviousstudy . . . . . . . . . . . . . . . . . . . . . . . . . 96
A.1 Tableofsamplestrategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
A.2 Descriptivestatisticforallvegetationsamples.. . . . . . . . . . . . . . . . . 110
A.3 Descriptivestatisticforallsoilsamples. . . . . . . . . . . . . . . . . . . . . . 111
vii
viii LISTOFTABLES
A.4 Levelsof11inorganicelementsinsoil . . . . . . . . . . . . . . . . . . . . . . 112
A.5 Levelsof11inorganicelementsinvegetation . . . . . . . . . . . . . . . . . 113
A.6 ResultsofPCBanalysisinsoil . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
A.7 ResultofPCBanalysisinvegetation . . . . . . . . . . . . . . . . . . . . . . . 115
A.9 LoadingsforvariablesinFA(A) . . . . . . . . . . . . . . . . . . . . . . . . . . 116
A.8 ShapiroWilktestfornormaldistribution.Forsoilandvegetationsamples.
Sampleswithp>0,05showanormaldisribution. . . . . . . . . . . . . . . . 117