Beruflich Dokumente
Kultur Dokumente
1. Introduction palaeomagnetic
studies,
wherethemainconcernis with domi-
nant remanencecarriers,rather than with the full range of en-
Over the last few years,environmentalmagnetistshave made vironmentallysignificantsignatures
and their variations.
increasinglyconfident interpretationsof their resultsin terms In mostpublishedrockmagneticstudiesof recentsediments
of defined magnetic mineral and grain size components [cf. andsoils,thatpartof the magnetic"signature" attributableto
Oldfield, 1991, 1994; Hounslow and Maher, 1996; Walden et imperfectantiferromagnetic mineralsis usuallyascribedto
al., 1999]. This is especiallytrue in the caseof the contribu- hematite[e.g.,Thompson and Oldfield,1986]. This practice
tions to rock magneticpropertiesmadeby ferrimagneticmin- may be explained,in partat least,by the customaryuseof 1 T
erals, sincethey frequentlydominatethe recordwheremagnet- as the maximumDC field available for remanenceacquisition
ite, maghemite, or greigite is presenteven in extremely low duringthe courseof routinemeasurement in many laborato-
concentrations.Much less attention has been devotedby en-
ries, coupledwith publishedindicationsthat in the caseof
vironmental magnetists to the common imperfect antiferro-
goethite,significantremanenceacquisitionbeginsabovethis
magneticminerals,hematiteand goethite.In the caseof mixed field (Dekkers,1988;Lowrie and Heller, 1982].
magnetic mineral assemblagesit is important, in environ-
Failureto distinguish
betweenhematiteandgoethitein rock
mental magnetism, to distinguish between the contribution
magneticstudiesof contemporary soils, palaeosols,andre-
that a mineral, or grain size class, may make to the magnetic
centsediments significantlylimits the interpretationof the
propertiesrecordedand the proportion of the bulk magnetic
results. Moreover,adoptingthe quasi-convention of ascrib-
mineral assemblageit constituteson a mass or volume basis.
ing "hard"remanence components to hematite,withoutcon-
This highlightsthe importanceof the imperfect antiferromag-
firmatoryevidence,mayactuallydistortpalaeoenvironmental
netic minerals in environmental magnetism, since their con- reconstructions,
sincethe two minerals,while often occurring
tribution to the mineral assemblageis almost invariably un-
togetherin soils and weatheringprofiles, tend to indicate
derrepresented, often by 1 or 2 ordersof magnitude,in the rou-
rather different geochemicalcontrols. Predominanceof
tinely measuredrock magnetic properties that provide the
goethiteoverhematitein the regolithis favoredby cooler,
main basisfor interpretation. This mattersmuch less in most
moremoistandorganic,andlessalkalinesoil-formingcondi-
tions [Schwertmann,1985, 1988a, b]. Thesemineralsalso
occurin different"primary,"unweathered, lithological con-
Nowat Department of Geography, ChesterCollege
of Higher texts.The relativeimportanceof the two mineralsin the mag-
Education Chester.England.United Kinedom. neticmineralogy of sedimentary rockshaslargelybeendocu-
2Nowat'PAGES ProJect Office,Bern,Switzerland
mentedthroughpalaeomagnetic studies. Thesecontrast,for
example,theimportance
of hematiteasa remanence
carderin
Copyright2000 by theAmericanGeophysical
Union. redbeds [Creer, 1962a; Collinson, 1974; Channell et al.,
Papernumber1999JB900304. 1982] with that of goethitein somelimestones[e.g., Lowrie
0148-0227/00/1999JB900304 $09.00 and Heller, 1982]. Very little researchhas been devotedto
2781
2782 FRANCE AND OLDFIELD: GOETH1TE AND HEMATrlE IN SOILS AND SEDIMENTS
characterizing
anddistinguishingthe two mineralsmagneti- 2. Sample Set
cally in soils and sediments.
Several methods are available for discriminating between The samplesconsideredhere includeore and synthetic sam-
goethiteandhematiteon the basis of their rock magnetic ples of goethite andhematite (and mixtures derivedfrom the
properties.Resultsfrom studiesof syntheticsand pureores synthetics)and a wide variety of soilsand sediments.The ores
suggestthat in relatively simple situations,room temperature and syntheticswere part of a larger setconsideredmore fully in
measurements alone may suffice. Relative to hematite, France [1997]. Soil and sedimentsampleswere first selected
goethitehas a higher saturatingfield (generally,>6 T), a on the basis of previously completedmagneticmeasurements
higher coercivityof remanence, and a lower saturationiso- on all the samples stored in the Environmental Magnetism
thermalremanentmagnetization(SIRM)/z quotient[Dekkers, Laboratory of the Department of Geography, University of
1988]. Evenmorediagnosticis the thermomagnetic behavior Liverpool. The main criterion for initial choice was the dem-
of the two minerals[Dekkers, 1988, 1989a, and b]. In the pre- onstratedpresenceof a significant remanencecardedby min-
sent studywe usehigh field remanenceacquisitionand ther- erals with a coercivity of isothermal remanencein excess of
momagnetic behavioras the basisfor discriminatingbetween 100 mT. Routinemagneticmeasurements, as describedby Old-
them. field [1991] and explained by Oldfield and Yu [1994] and
The aimsof thepresentstudyare(1) to adaptpreviouslypub- Chenet al. [1995], were then usedto screenthe initially cho-
lishedmethods,largely developedfor the studyof oresand sen set of 120 samples and to identify 60 for further study
syntheticsamples,to the identificationof goethiteand,where [France, 1997].
possible, thediscriminationof hematiteandgoethitein a wide The main criteria for selecting soil and sediment samples
varietyof naturalsoilsandsediments, eachcontaininga rela- from the initial set for more detailedstudieswere (1) the pres-
tively complexmixtureof magneticphases, (2) to derivefrom ence of a significanthard remanencecomponent, here consid-
the obtainedresultsthe rock magneticcriteriafor confirming ered as that percentageof total SIRM (=IRM1T) acquiredabove
the presence of goethitewhereit is a significantcontributorto +300 mT, or remaining unreversedin a backfield of-300 mT
the magneticpropertiesof naturalsamples,and(3) to makea (in sampleswith a high SIRM a lower percentageof the hard
preliminary assessment of the extentto whichgoethite,iden- remanencewas acceptedthanwas the casein weakly magnetic
tified in thisway, may contributeto the hardremanence com- samples) and (2)variety of provenance,both geographically
and in terms of environmental context. Table 1 summarizes
ponentin rockmagneticstudiesof soilsandsediments.
Sincethe mainmaterialsusedin the studycametoma set of the provenanceof the samplesconsideredin the presentpaper.
soil andsedimentsamplesalreadymeasured andarchivedover They were selectedas representative of the 60 samples sub-
a periodof 20 yearsas a resultof a widerangeof research in jected to the same sequenceof measurementsthe results of
which are describedin France [1997].
environmentalmagnetism,contextualinformationregarding
soilchemistry andpH hasnotbeenavailable.Nor wasit often
possibleto testinferencesbasedon rock magneticmeasure- 3. Methods
mentsagainsttheresultsof moreconventionalmethods,such
asX-ray diffraction(XRD) sincein mostof thenaturalsamples The following procedureswere adopted:
studiedhere the concentrationsof magneticmineralswerefar 1. High field acquisitionof isothermal remanentmagnetiza-
too low. tion was carriedout on subsamples (mass300 mg) packedinto
Samplecode Provenance
G1 and H1 goethite(G1) andhematite(HI) ore (suppliedby LiverpoolMuseum)
IG syntheticgoethitepowder(suppliedby I. Lamey)
E3014 synthetichematitepowder(suppliedby B. Maher)
Ratio 1:1, 29:1, artificialmixturesof synthetic
goethitepowderF7041 andsynthetichematitepowderE3014 (suppliedby B.
and 49:1 Maher)
L60 and L61 a deeproadside
cuttings
in Lateriteon PalauBatam,Indonesia,
reflectthemaximumcolorcontrast
of the yellow
L60 and the pink coloredL61 samples
MR 1/2 Portuguese
coastalsitebetweenMilfontesandPortoda Barcasrepresenting
an exposedcliff top sectionwhich
lies beneatha recentlymobilized dune
SA 2/10 a Plioceneor Quatemarydepositin the St. Domingoroadcutting,Alualade,Portugal
RC and YB Chinesesoil classification
krasnozem(red soil) from Jiangxiand zheltozem(yellow soil) from Guizhou,China
D 34 DianchiLakeis anopenlaketo thesouthof thecity of Kunming,China;sampleD 34 a particle-sizedclay
fractionof the sedimentfrom a depthof 9.5 m
RR5a and contemporary blackbeachsandRR5a andtheMioceneagemarlRRMC originatefrom theRhodeRiver, a
RRMC tributary of the ChesapeakeBay, southof Annapolis,Maryland
H 357 and SatalLake in theIndianHimalayanfoothills,sitefromwhichtwo particle-sizedclay fractionsedimentsamples
H365 were obtained
URS 8D and UrswickTam (URS 8D) and Red Tam, Langdale(RT6), in Cumbria(NW England); extensivereported
RT6 hematiteminingin thisarea.
LP 3/10 and Loe Pool,a eutrophiccoastallakenearHelston,southwest England,intowhichextensiveminingwastewas
LP 3/26 depositedduringthe early twentiethcentury
MAP 12 and 65 turbiditesamplesfromtheMadeiraAbyssalPlainstationD10688, showingevidencefor reductive"suboxic"
diagenesis
PTA slowdesiccationduringstoragediagenesis of an artificialsediment/ soilmixture;soilobtainedfrom Broadway,
Gloucestershireand sedimentfrom PeckfortonMere, Cheshire,England
FRANCE AND OLDFIELD: GOETH1TE AND HEMATITE IN SOILS AND SEDIMENTS 2783
50
-50
-100
-150
-200
0 10 20 30 40
Time (minutes)
10 mm x 25 mm long cylinders. Stepwiseacquisitionof iso- mitted changesin IRM to be plotted against rising tempera-
thermalremanentmagnetization
(IRM) up to 7 T wasachieved ture.
usingthefollowingsequence of fields:10-40mT (at 10-mTin- 5. A separate--1-g subsamplewas usedfor thermal demag-
tervals);60-100 mT (at 20-mT intervals);150 mT; 200-400 netization experiments. In these, each samplewas dispersed
mT (at 100-mT intervals);600-1000 mT (at 200-mT inter- in a heat-resistantfurnacecementwhich couldthen be placed
vals); 1500 mT, and2000-7000 mT (at 1000-mTintervals). in a rubbermoulddesignedto fit into boththe largerof two ex-
Fieldsweregenerated in a 10-mminternaldiameterexternal ternal coils attachedto the Trilec CDM (generatinga peak DC
magnetizer(CDM) manu- field of 4 T) and the minispinmagnetometer.
coil linked to a capacitordischarge
facturedby Trilec Instruments. 6. After orthogonaldemagnetization in a DC field of 400 mT
2. Orthogonal DC demagnetization[cf. Lowrie,1990]in a (see above) both the hard and soft IRM components were
field of 400 mT was usedto remove the influence of ferrimag- monitored during stepwise thermal demagnetization in 10
neticgrainson the remanence acquiredin the originaldirec- stages
from50Cto 680C.Thepreviously
determined
and
tionof magnetization.
Thiswasachieved by placingthe sam- highly consistentresponseof the heat resistantmatrix to the
plesin a Molspinpulsemagnetizer, eachsampleorientedso heatingexperimentwas usedto providethe basis for adjusting
thatanyIRM acquired in the 400 mT field wasat right angles the measurementsso as to exclude its contribution. Low-field,
to the original IRM?T. This allowed its subsequentmeasure- low-frequency
(0.47 kHz)magneticsusceptibility(Zlf) was
ment as a separate,"soft" componentof the IRM in the alsomeasuredat each stagein the heating experiments,using
minispin magnetometer.A field of 400 mT was usedfor or- a BartingtonMS 2 meteranddual-frequency sensor,in ordert o
thogonaldemagnetization in orderto reduceto a minimum any provideevidencefor any thermally inducedchangesin mag-
chanceof ferrimagneticcontributionsto the hard component. netic mineralogy. In most of the naturalsamplesconsidered
3. The cylindricalsampleswerethenmountedin a polytetra- here, thesechangeswill includethe effectsof combustingor-
fluoroethylene (PTFE) cube and brought to liquid nitrogen ganic matter present in the samples, and the results are not
temperature (-196C) withinzerofield. consideredfurther in the presentpaper.
4. The sampleandPTFE holderwerethen quicklytransferred The flow diagram in Figure 2 summarizesthe sequenceof
to a minispin low speedspinnerfluxgate magnetometer,and measurements performed.Full detailsof theseandof ancillary
the changesin the hard remanence(i.e., that acquiredand re- measurements using empty holdersand the heat resistant ce-
tained in the original directionof magnetization)during warm- ment are given in France [1997].
ing to roomtemperatureweremonitoredautomaticallyat 10-s
intervals over a 40-min periodwhile the sample remainedin 4. Criteria for Mineral Identification
zero field within the mu-metal shielding in the magnetometer.
Direct temperature recordingby thermocouple duringthis pe- Theexperiments describedabovewerechosen from a range
riod wasprecludedby the spinningof the sampleduringmeas- of possible approaches,andtheyareessentially modifications
urment. Instead,the resultsof previous time-temperaturecali- of the methodsusedby Heller [1978], Lowrie and Heller
bration experimentsusing identicalapparatus(Figure 1) per- [1982],andDekkers[1988,1989a,b] to identifygoethiteand
2784 FRANCE AND OLDFIELD: GOETHITE AND HEMATITE IN SOILS AND SEDIMENTS
BULK SAMPLE
I --
I
I
I
I
Routine magnetic I
measurements I
I
I
Stepwise
Low-temperature
Mr measurements
therma demagnetization
of IRM
I
I
I
Susceptibility Orthogonal DC High-field IRM
High-field
IRM
I
z, & Xhf acquisition up to 7 T demagnetization Acquisitionat 4 T
I
at 400mT
I
I
I
I
Choice of samples Immersion in
ARM for further
liquidnitrogen
experiments
Stepwise
heating
upto
680C and coolingin
I
"1zero
field
ateach
step
I Restoration to room
Stepwise Measurement of
I
acquisitionof IRMT temperature while susceptibilityat
I
measuring
Mr every10s each step
I
I
I Measurementof Mr
I in "hard" and "soft"
Stepwise D.C. I Conversion of the
vectors
demagnetization I timescale to
of IRMT I temperature
I
I
I
Plots of mass Plotof "hard"Mr Plot of "soft" and "hard"
specificparameters against Mr and susceptibility
and quotients temperature against temperature
moto, 1958; Yamamoto, 1968]. Dekkers and Linssen [1989] an orthogonal field high enough to exclude all ferrimagnetic
suggestthat a smearedMorin transition is dueto surfaceef- mineralsfrom the original direction of magnetization. There
fectsof absorbedsilica andwater. Despitethe ambiguitiesin also remainsthe possibiltyof nonorthogonally allowing sig-
the publishedliterature,it is reasonable
to infer that a signifi-
nificant "leakage" of a strong ferrimagneticphase into the
cantdecline in hardMr from-196C to roomtemperature is a hard signal.
reliable indicatorof goethite,and a Morin transitionanywhere In the presentstudywe have concentratedon two aspectsof
between approximately -70C and-15C is a reliable
indicator the thermaldemagnetizationcurves:(1) percentageloss of the
of hematite.Quantitativemineralogicalor magneticgrain size hard, orthogonallydemagnetizedroom temperatureIRM4, be-
inferencesfrom the steepnessof the declinein temperatureor low110C and(2)thepercentage of theorthogonally demag-
the natureof the Morin transition, where present, have not netized, hard, room temperature IRM4, remaining above
been attempted.It is importantto stressthat in the low-tem- 600C.Highvalues fortheformeraretakento indicate the
peraturehardremanence experiments,positive indicationsof greater relative importance of goethite (Curie temperature
the presence
of goethite,in the absenceof a Morin transition, 120C),
forthelatter,hematite
(Curietemperature
675C).
do not confirmthe absenceof hematite: the latter may be pre-
sentalongsidegoethitebut in a form that doesnot give rise to
a Morin transition.In this case, it is likely that the presence 5. Results
of hematitewill be indicatedmost clearly by the thermal de-
5.1. Ores, Synthetics, and Mixtures
magnetizationexperiments.
3. In the absenceof independentinformation on magnetic The XRD spectra (Figure 3) confirm the relative purity of
grainsizeanddomainstate,evidencefrom the thermaldemag- both the synthetic samplesas well as the hematite ore. The
netizationof even the hardcomponentof the IRM may needto goethite ore sample is seen to contain some hematite con-
be viewed with cautionsinceit is conceivablethat unblocking tamination.The resultsof the experimentson the two ores and
temperatures for someof the hematitepresentin a samplemay two synthetic samples (Figure 4) illustrate the typical rock
lie below the N6el temperatureof goethite. The situation is magneticresponsesof goethite and hematite. In the case of
muchmorecomplexin the caseof the orthogonallyaligned the hematite synthetic, there is rock magnetic evidencefor
soft IRM, sinceit may be influencednot only by ferrimagnetic somecontaminationby a ferrimagneticphasenot detectedby
components in the samplebut also by low-coercivity goethite XRD. Clear differencesin saturatingfield (Figure 4a), in the
of choosing sequence
andhematite.This is an inevitableconsequence of Mr -versus-temperature
changes
from-196Cto
G1 H1 H
e-
H H
!
I[ Q30I !d
1 50j[ i
HH
o 0 20 40 60
IG E3014
G
e-
H
H
io 50 o lO 20 50
Degrees 2 0
F7401
e- G = Goethite
G
H = hematite
Q = quartz
i
i
G i
G
30 40 50 0
Degrees 2 0
Goethite Ore (G1) Synthetic Goethite (IG) Hematite Ore (H1) Synthetic Hematite (E3014)
(a) lO
250
200
150
600
200
800
100
50 400
o r--- i i 0 0
0.01 0.1 1 10 0.01 0.1 I 10 0.01 0.1 1 10 0.01 0.1
Appliedfield(T)
1.7 1.0
(b) 2.5
2.2 1.5 0.9
o
:2 1.9
0.8
: 1.6
0.7
: 1.3
i t i i 0.6 i I i i
1.0
-200 -150 -100 -50 0 50 -200 -150 -100 -50 0 50 -200 -150 -100 -50 0 50 -200 -150 -100 -50 0 50
TemperatureC
0 200 400 600 800 0 200 400 600 800 0 200 400 600 800 0 200 400 600
Temperature C
lOO 2
(a) 1:1 29:1
-- 80-
9 49:1
E 60
6
E
; 40-
3
20-
o 0
O.Ol 0.1 I 10 0.01 0.1 1 0.01 0.1 1
Appliedfield(T)
0.8
-.-.-----
29:1hard
g o.8 -,, 29:1soft ,,,' - 0
0.8
E
o
0 0.6 0.6 0.6
:::3
i i i
z 0 0 0 o
0 200 400 600 800 0 200 400 600 800 o 200 400 600 80O
TemperatureC
2.0
(c)
"-.,..,.. Goethite SampleF7401 .......... Goethite
......,..._. Hematite SampleE3014
............... Goethite 49:1 Hematite
1.6
-\
0.8-
0.4-
0
-200 -150 -100 -50 0
TemperatureC
Figure 5. Resultsfor synthetic goethite: hematite mixtures. (a) The Mr versusfield strengthgraphsshow
significantacquisitionabove 4 T only when the goethite componentsignificantly exceedsthat of hematite.
(b) All the mixtures show a two-stagethermal demagnetizationprofile with the relative importance of the
lowertemperature
step(to 150C)
morestrongly
marked
in thegoethite-dominated
mixtures.
(c)TheMorin
transitionis apparentin all the mixturesbut the declinein Mr with increasingtemperature,typical of goethite,
is only presentin the goethite-dominated mixtures.
(a) 3
o.6.
/
0 t I
10 0.01 0.1 1 10 0.01 0.1 1 10 ).01 0.1 1
Appliedfield(T)
(b) 3.0
2.6
:14
1.8
lO
-2oo -15o -1 -50 0 50
11
019i i
-200 -150 -100 -50 0 50
TemperalureC
.200
i
-150
i
-100
i
-50
I
0 50
i
-200 -150 -100 -50 0 50
(c) 0.81-[
I, ha -" I ......
\
1.0
........
I\ ,;..... 112
0 soft ......
' /
,,..... 30D B
100
1.0
t ,/
50
40
o 00
Z 0 200 4 6 0 0 2 0 0 8 0 00 200 6 0 0 00 0
Temperature
oC
Figure 6. Laterite samplesfrom Palau Batam, Indonesia(L60 and L61), and soil samplesfrom Portugal (see
text). SamplesMR 1/2 and SA 2/10 have IRM acquisition, cooling behavior and thermal demagnetization
characteristics
typicalof gooethite.
Samples
L60andL61bothshowthe(consistent
though
lesssteep)lossof
M r on warmingfrom -196 C to room temperatureof goethite. In the caseof L60 and despite the unambiguous
thermal demagnetizationtrace, IRM acquisitionis much less distinctive. In L61 especially, both the IRM
acquisitionand hardM r thermaldemagnetization curve indicatea significanthematitecontribution.
tify goethite in either sample, they are consistentwith the hematite contribution to the soft IRM is apparent in the red
rock magneticresultsto the extent of giving a much stronger sample,but not in the yellow one.
signal for hematitein L61 than in L60. The third sampleshown in Figure 7 (D 34), is from the clay
The two Portuguesesoil samplesshown here (Figure 6, MR fraction of lake sedimentsamplefrom Dianchi Lake, Kunming
1/2 and SA 2/10) both show acquisitionof remanencecontinu- [Yu and Oldfield, 1990]. There is very little sign of continued
ing above4 T, especiallyin the caseof SA 2/10. Both show a acquisitionat 7 T, but some loss of cooled hard remanenceis
steep,monotonicloss of hard remanence,with over 80% loss clearly recorded.This, togetherwith the steep thermal demag-
by the time room temperatureis reached. Both samples also netization
below200C,also pointsto the presence
of
show steep thermal demagnetization of hard IRM below goethite, but some hard remanence also persists beyond
200C.Thesoftremanence
thermal results 600C,
demagnetization soa hematite
contribution
cannot
beprecluded.
for MR 1/2 were not reliable, but SA 2/10 clearly includesa The first two samplesshownin Figure 8 are from the shores
relatively soft componentthat is not fully demagnetizedbe- of the Rhode River, a small tidal arm of Chesapeake Bay.
low600C.All therockmagnetic
measurements
thusgive Sample RR5a is a beach sand from beneath an eroded cliff
consistentindications of the importance of goethite in both formedof poorly consolidatedEocenesandsof the Nanjemoy
samples, with some possible indication of hematite in SA formation. Despite the lack of IRM acquisition above 2 T,
2/10. The XRD spectrumfor that sample reveals no goethite thereis a dramaticloss of cooled hard remanenceon warming
and only a traceof hematite. (over 65%), as well as a significant decline in both hard and
Figure7 includesdata from two subsamplesof Chinese "ref- softremanence
below200C
onthermal
demagnetization.
The
erence" soil monoliths [Yu, 1989], the "C" horizon of a "red presenceof a goethite phase with an uncharacteristicallylow
soil" (RC) and the "B" horizon of a "yellow soil" (YB). Both Mrs is indicated, though both the thermal demagnetization
show continuedremanenceacquisition at 7 T and significant curvesand the XRD results(Figure 11) also confirm the pres-
lossof cooled
hardremanence
onwarming
to20C.Thisis es- ence of hematite. Sample RRMC is of Miocene Marlboro
pecially notable in the yellow soil subsample.The thermal Clay. The remanence acquisition curve fails to confirm
demagnetizationgraphs show two distinct component in the whether or not goethite is present, but the steep, monotonic
hard IRM, one typical of goethiteand one of hematite. A clear loss of cooled, hard remanence reduces the initial value to
FRANCE AND OLDFIELD: GOETH1TE AND HEMATITE IN SOILS AND SEDIMENTS 2789
RC YB D 34
(a) 25 .5 6
20
E 10
I ,
o i m_
Appliedfield (T)
,.5
(b) 1.4
1.o i .0 I I , i i , i
-200 -150 - 100 -50 0 50 -200 -150 -100 -50 0 50 -200 -150 -100 -50 0 50
Temperature C
100 .
Temperature C
Figure 7. Soil and sedimentsamplesfrom China. (a) The IRM acquisitioncurvegives little indication of
which hard remanencemineral is dominant. (b) All samplesshow steep loss of hard Mr during warming to
roomtemperature,
(c)aswellassteeplossof hardMr below150Cduringthermal
demagnetization.
Further
lossof remanence
continues
beyond600C, indicatingsomepresence
of hematite
in eachsample
alongside
the goethite.
<50%. This, coupledwith the loss of almost 50% of the hard netization curvesare dominatedby hematite-typebehavior.
remanencein the first stepsof thermal demagnetization,con- The two samplesfrom Loe Pool in Cornwall are also of hema-
firms the presenceof goethite.Survival of a significantpart of tite mining waste,but in both cases,thoughmoreespecially
boththesoftandhardremanence
components
above600C the first, there is some indication of a net loss of cooled hard
showsthat hematiteis also present. remanenceon warming,uponwhich a strong Morin transition
SamplesH 357 and H 365 are clay size fraction subsamples is superimposed.Both samples also show indications of a
from Saatal, a small lake in the northern Indian Himalayas. two-phaseresponseto thermal demagnetization,with over
The thermaldemagnetizationexperimentfor the latter sample 20% of the initial remanence
lost below200C.The results
failed to providea coherenttrace.In both cases,the IRM satu- point to detectablegoethitecomponentalongsidethe clear in-
rates at or below 2 T, and there is no sign of any changein dicationsof hematitein both these samples.XRD tracesfor
cooled hard remanenceon warming. Hematite is the only URS 8D and LP 3/10 both show signs of hematitebut not of
phaseclearly indicatedby the thermal demagnetizationtrace goethite.
for H 357. Thesesubsamplesexemplify hematite-dominated The first two plots in Figure 10 refer to samplesfrom a tur-
assemblages lacking any evidencefor a Morin transition. bidite from the Madeira Abyssal Plain (MAP) that has been
The firsttwo samplesplottedin Figure9 are from smalllakes
stronglyaffectedby suboxicdiagenesis[Sahota et al., 1995].
in NW Englandinto which hematiteinwashduringthe period In both cases,there are signs of continuing acquisitionof re-
of nineteenthcenturymininghasbeenrecorded.In both cases, manericeat 7 T and of significant loss of cooled hard rema-
the IRM comes close to saturation below 5 T, there are nenceon warming. Theseindications are consistentwith the
strongly markedMorin transitions, and the thermal demag- steep loss of hard remanenceboth samplesshow well below
2790 FRANCE AND OLDFIELD: GOETH1TE AND HEMATITE IN SOILS AND SEDIMENTS
(a)
3 -
0 I I
0.01 0.1 1 10 001 0.1 1 10 0.01 0.1 1 10 0.01
Appliedfield(T)
2.4 2.6
1.0 _,_.__
2.2
1.6 1.8
0.9
1.4
/ I I 1.0 - i 08 ' I I I
-200 -150 -100 -50 0 50 -200 -150 -100 -50 0 50 -200 -150 -100 -50 0 50 -200 .150 -100 -50 o
Temperature C
hard ,--
oo 4 0 o 0 o o 0 2 ' 4 ' 8 o
Temrature C
200C
onthermal
demagnetization.
Theonlysignof thepos- lateritic soils. A significantgoethite contribution is indicated
sible presenceof hematiteis the persistenceof both a soft and in all the cases.This is truenot only for the presentsamples
hardremanence
component
beyond600C.Thefinal sample but also for the larger set consideredin France [1997]. This
(PTA) is a mixture of magneticsurfacesoil with sedimentfrom largerset also includesclay fractionsfrom deeplyweathered
Peckforton Mere in Cheshire, NW England. The mixture was colluvial materialtaken from a complexvalley fill in New
usedin experimentsto explore the effects of sample storage South Wales, Australia (H. Crockford, personalcommunica-
on magneticproperties[Oldfield et al., 1992]. The samplerep- tion, 1992). In most cases, there are also indications of a
resentedherereflectedthe effects of "storagediagenesis"over hematitecontribution to the rock magneticproperties,though
a periodof 3 years. Only the remanenceacquisitionand cool- the evidencefrom the magnetic measurements usedin these
ing experimentscould be completedon the material available. experimentsis not alwaysunambiguous. Even where,as in the
Some slight persistenceof acquisitionof IRM at 7 T is indi- caseof SA 2/10 (Figure6), all thelinesof evidence,high-field
cated, and the loss of cooled hard remanenceon warming is acquisition,
lossof cooledhardremanence, andrapidandal-
strongly marked, confirming once more the presence of mostcompletethermaldemagnetization
well below 150C,
goethite. convergeto give the strongestpossible signs of a major
goethitecontributionto the magneticproperties,the XRD
spectrumfails to detectthis, despiterecordingtracesof the
6. Discussion
magneticallymuchlessdominanthematitephase.This con-
6.1. Goethite in Soils flictswiththe inferencederivedfromthemixing experiments
alreadydescribed above. Whetherthe apparentcontradiction
The soils consideredin the presentstudyincludeMediterra- reflectsthefactthatthe syntheticsusedin the mixingexperi-
neansoilsdevelopedon a range of parentmaterials,subhumid mentsarequiteunrepresentative of naturalsamplesor the in-
semitropical and cool temperatesoils, and humid tropical sensitivityof XRD to the form in whichgoethiteoccursin the
FRANCE AND OLDFIELD: GOETH1TE AND HEMA IN SOILS AND SEDIMENTS 2791
(a) 50 3O 8
6
20
0I
0.01
0.1
1 10 001 0.1 1 10 001 0.1 1 10 0.01 0.1 1 10
Appliedfield(T)
0.8 1.2
0.7
1.00
/
:04 0.6
05
1.1
1.0
0.96[
0.92
-50
i
0
,
50
O4
O3
-200 -150 -100 -50 0 50
0.9
0.8
-200
i
-150 -100
i i
-50
i
0 50
0'88
f
0.84
0.80
-200 -150 -100 -50 0 50
TemperatureC
I \ \ , o11
, I/'",._
o.,[ / , o.,
r / o.,
, r / / .
............ 40 ................ 1
0.2
0
/' 3 0 -,-.......T...........[
0
0.2 -'"'/
00 0 0
0 2 4 0 0 2 0 0 2 0 0 8 0 2 0 8
Temrature C
naturalsamplesusedcannotbe resolvedfrom the data pre- to goethite seems less likely [Berner, 1969; Langmuir,
sentedhere. Rock magneticconfirmationof the presenceof 1971]. In all three cases considered above, the sediments are
goethitein all the soil samplesstudiedis not surprisingin unlikely to be more than 200 yearsold [Oldfield and Statham,
light of the observationsof the iron chemistryof soils sum- 1963; Simola et al., 1981].
marizedby Schwertmann[1985, 1988a, and b] and Schwert- The clay fraction from the Dianchi lake sediments [Yu and
mann and Taylor [1989]. Oldfield, 1990] first alertedus to the possibility that goethite
may be contributingto the magneticpropertiesof these sedi-
6.2. Lake Sediments ments as a product of weathering under humid, subtropical
conditions, since the hard remanencecomponent was most
In the caseof UrswickTam andRedTarn, both in parts of
strongly representedin the clays, which were ochre in color.
Cumbria(NW England,)wherehematitemining hasbeenwell
documented, the hematitecharacteristics,as expected,domi- Confirmation of this inference by rock magnetic measure-
ments is consistent with the results from the Chinese soils. In
nate the magnetic properties. In the case of the Loe Pool
(Cornwall,SW England)sediments, chosenin the expectation provenance-orientedrock magnetic studies of sediments, it
of closelycomparableresults,the sampleset includesmaterial servesto emphasize the need to understandand characterize
with a recognizablegoethitecontribution. SamplesLP 3/10 rock magnetically, the weathering regimes, and productsin
andLP 3/26 (Figure9) showclearsignsof a mixed mineral as- the region, rather than rely on analogieswith evidencefrom
semblagebroadly comparableto those createdin synthetic other pedoclimatic zones. Hematite properties appear to
mixturesamples2 and3, wherethe goethiteproportiondomi- dominatethe two samplesfrom Saatal(a small, artificial lake
nates in mass terms. From the evidence available, it is not in the HimalayanFoothills),which also lack any positive in-
possibleto say whetherthis reflectsdetritalgoethitedelivered dication of goethite.
to thelake as part of the wasteinwashfrom mining upstream
6.3. Effects of Diagenesis
or the pedogenictransformation of hematiteto goethiteeither
in the uplandsoils of the catchment[cf. Schwertmann,1971] Severalauthors[e.g., Bloemendalet al., 1992] have observed
or duringstoragein waterloggedvalleyfill at the inflow to the that during reductive (suboxic) diagenesis[Froelich et al.,
lake. Postdepositionaldiagenetictransformationof hematite 1979], there is usually some selective persistenceof the hard
2792 FRANCE AND OLDFIELD: GOETH1TE AND HEMA IN SOILS AND SEDIMENTS
(a) 2.0 ,
1.6
E 0.8
_a:_:
0.4
o I i I
O.Ol 011 1 10 0.Ol 0.1 1 O.Ol 0.1 1 lO
Appliedfield(T)
(b) 2.8
o 2.3
- 1.8
,-. 1.:3
0.8
-200
__ I
-150
I
-!00
I 1
-50 0 50 -200
I
-150 -100
I I
-50 0
i
50
,
-200
i
-150 -100
i
-50
I I
0
TemperatureC
Figure10. Diagenetically
altered
sediments
fromtheMadeiraAbyssal
PlainandfromPeckforton
Mere.In
all cases
thelow-temperature results
in thethermal
demagnetization
curves (whereobtainable)
suggest
that
goethiteis a significant
contributor
to thehardremanence
components
in thesediments.IRM acquisition
alone giveslittleindication
ofthemineralogy
ofthehardremanence
componentsin thesesamples,
though
in
all cases,someacquisitioncontinuesabove4 T.
L$O URS 8D
o[ Q
Q H
H
o o o c:;o ;o o o o o
L 61
I LP
3110
I C
C
H H Gi . C I HII Q C
i
10 20 30 40
Q Q C = Chlodte
SA 2/10
K = Koalinite
Q Gi = Gibbsite
H = Hematite
I QQ I= Illite
Q Q Q = Quartz
. !
i I i i
40 ,50 60 10 )0 40 50 60
Degrees2 0 Degrees2 0
Table2. Summary
oftheDiagnostic
Magnetic
Properties
oftheNatural
Samples
UsedinthePresent
Study
andofthe
Categories
toWhich
theHardRemanence
Carriers
Present
inEachSampleMayBeAscribed
Sample
Name Sample
Code Figure Hs,T Mr.196/M
r Mrllo/M
r Mr6oo/Mr Category
Goethite
ore G1 4 >7 2.40 0.02 0.00 G
Hematite
ore H1 4 5 0.23 0.98 0.90 H
Synthetic
goethite IG 4 >7 1.58 0.61 0.00 G
Synthetic
hematite E3014 4 3 0.03 0.83 0.21 H
Arfificalmixtures ratio1:1 5 5 0.08 0.82 0.18 M
ratio29:1 5 >7 0.96 0.57 0.15 M
ratio49:1 5 >7 0.97 0.58 0.15 M
Indonesia,
Palau
Batam L60 6 5 2.75 0.39 0.00 M
L61 6 >7 1.62 0.82 0.40 M
Portugal,
Alentejo MR1/2 6 >7 5.50 0.38 0.00 G
SA 2/10 6 >7 4.60 0.20 0.03 M
China,
RedSoil RC 7 >7 1.33 0.52 0.18 M
China,
Yellow
Soil YB 7 2 3.20 0.53 0.18 M
China,
Dianchi
Lake D 34 7 3 1.34 0.78 0.04 M
United
States,
RhodeRiver RR5a 8 1.5 2.75 0.78 0.11 M
RRMC 8 6 2.70 0.52 0.13 M
Indian
Himalayan
foothills H 357 8 3 0.88 0.93 0.46 H
H 365 8 3 0.98 N/A N/A H
United
Kingdom,
Urswick
Tam URS8D 9 3 0.23 0.93 0.48 H
United
Kingdom,
RedTam,LangdaleRT6 9 7 0.31 0.92 0.10 H
United
Kingdom,
LoePool LP3/10 9 >7 1.15 0.79 0.28 M
LP 3/26 9 6 0.97 0.87 0.18 M
Madeira
Abyssal
Plain MAP12 10 5 2.40 0.73 0.00 G
MAP 65 10 4 1.80 0.56 0.04 M
United
Kingdom,
Peckforton
Mere PTA 10 2 1.75 N/A N/A G
Hsisthefieldstrength
atwhich
theIRMsaturates.
Mrorefers
tothehard
remanence
component
remaining
afterorthogonal
demagnetiza-
tioninafieldof400mT. Subscripts
refertotemperature
C.G,goethite;
H,Hematite;
M, mixed
G + H. N/A,notavailable.
2794 FRANCE AND OLDFIELD: GOETH1TE AND HEMATITE IN SOILS AND SEDIMENTS
Rochette,
P., andG. Fillion,Fieldandtemperature'
behaviour
of rema- Thompson,R., and F. Oldfield, EnvironmentalMagnetism, Allen and
nence in syntheticgoethite:Paleomagnetic
implications,Geophys. Unwin, Winchester, Mass., 1986.
Res. Lett., 16, 851-854, 1989. Walden, J., F. Oldfield, and J. Smith(Eds.), EnvironmentalMagnetism:
Sahota,
J.,S.G.Robinson,
andF. Oldfield,Magneticmeasurements
used A practical guide,Tech. Guide 6, Quat. Res. Assoc.,London, 1999.
toidentify
oxidation
frontsin deepseasediments
fromtheMadiera Yamamoto,N., The shift of the spinflip temperatureof -Fe20 3 fine
Abyssal
Plain,Geophys.Res.Lett.,22,1961-1964,
1995. particles,J. Phys.Soc.Jpn.,24, 23-28, 1968.
Schulze,
D.G.,Theinfluenceof aluminiumonironoxides,VII, Unit cell Yu, L., Environmentalapplications of mineral magnetic measurements:
dimensionsof Al-substituted
goethites
and estimation of AI from Towards a quantitativeapproach,Ph.D. thesis,Univ. of Liverpool,
them,ClayClayMiner.,32, 36-44,1984. Liverpool,England,1989.
Schwertmann,U., Transformation
of heamatiteto goethitein soils,Na- Yu, L., and F. Oldfield, Palaeoenvironmental implicationsof magnetic
ture, 232, 624-625, 1971. measurementson sedimentcore from Kunming Basin, southwest
Schwertmann,
U., Theeffectof pedogenic
environments
on ironoxide China, J. Pateotimnot., 3, 95-111, 1990.
minerals,Adv. Soil Sci., I, 171-200, 1985.
Schwertmann,U., Someproperties
of soilandsynthetic
ironoxides, in,
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editedby J.W.Stucki
et al.,pp. 203- D. E. France,Departmentof Geography,ChesterCollege of Higher
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Schwertmann,
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editedby F. Oldfield, PAGES Project Office, B'arenplatz2, Ch-3011, Bern,
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et al.,pp. 267-308,D. Reidel,Norwell,Mass.,1988b. Switzerland.(frank.oldfield@pages.tmibe.ch)
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