Iron sulphides and their effect on the XRFmeasurement of the bulkchemical composition of badland soils near the Karabash coppersmelter Southern Urals Russia

Yury N Vodyanitskii1 TatianaMMinkina2 Stanislav P Kubrin2 ampVitaly G Linnik131 Lomonosov Moscow State University 1 Leninskie Gory 119991 Moscow Russia2 Southern Federal University 105 Bolshaya Sadovaya street 344090 Rostov-on-Don Russia3 Vernadsky Institute of Geochemistry and Analytical Chemistry Russian Academy of Sciences 19 Kosygin street119991 Moscow RussiaTMM 0000-0003-3022-0883

Correspondence tminkinamailru

Abstract The determination of the bulk chemical composition of sulphide-containing soils and badland soils causesdifficulties by X-ray fluorescence (XRF) analysis the content of sulphur is underestimated The inability to determine the mainelement oxygen is the reason for errors in the XRF bulk chemical analysis of the badland soil A procedure is proposed for theadjustment of oxygen content in the solid phase of the badland soils using Moumlssbauer spectrometry data on the content of Feminerals The contents of total iron sulphur and oxygen in the soils can be corrected in the case of simple iron mineralogyAfter correction the total content of sulphur measured by XRF significantly increases and that of oxygen decreases Theclarified oxygen content of the solid phase of badlands soil can be used to characterize the degree of their degradation

Keywords sulphide-containing soils mineralogy pollution Moumlssbauer spectrometer X-ray fluorescence spectroscopy

Received 24 October 2017 revised 5 February 2018 accepted 5 February 2018

Environmental disturbances caused by human activities such asopen cast mining have a profound effect on the dynamics andfunctioning of ecosystems (Arenas-Lago et al 2014) The Tourocopper mine (Galicia NW Spain) was operated between 1973 and1988 The geological substrate is amphibolite with significantamounts of metallic sulphides such as pyrite pyrrhotite andchalcopyrite (Aacutelvarez et al 2010 Cerqueira et al 2012) Today thesoils formed on the settling pond and on the mine spoils haveserious problems as a result of acidic drainage and extremely highconcentrations of heavy metals (Asensio et al 2013 Arenas-Lagoet al 2014) amongst others

The enterprises causing the maximum environmental damageinclude copper smelters and among them the Karabashmed coppersmelter located in the Southern Urals (Makunina 2001 Udachinet al 2003 Kalabin amp Moiseenko 2011) The development of theKarabash antropogenic anomaly started in 1910 when the coppersmelter began to operate

Since the operation of the smelter in 1910 two anthropogeniczones have formed in the surrounding area of 30 km2 the badlandsand the zone of tolerant vegetation (Makunina 2002) The zone ofanthropogenic badlands includes the area of the smelter itself andthe Karabash Ridge with adjacent low-mountain areas on theZolotaya Mount slope

Refuse ores from the Karabash pyrite orebody filled tailingdumps where fine aluminosilicate and sulphide particles containingup to 30ndash50 pyrite are stored Until 1952 this refuse ore (about 6million tons) was discharged into the Sak-Elga River withoutpurification which resulted in the formation of an anthropogenicdesert The desert area is c 25 km2 the badland soils depth is from02ndash03 to 20 m (Aminov amp Lonshchakova 2009 Ulrsquorikh ampTimofeeva 2015)

The exact knowledge of the total sulphur content is necessary formonitoring the state of the soils The importance of sulphurdetermination for soil monitoring is that anthropogenic sulphur

comes into the soil in the form of sulphides (mainly iron sulphides)which is unusual for automorphic soils The oxidation of sulphidesto sulphuric acid strongly increases the acidity of soil Theexceedance of the background content of sulphur is the mostintense feature of badland soil contaminated with iron sulphidesThe bulk chemical composition of soils is generally expressed in theform of element oxides The sum of macro-element oxides(including sulphur oxide) is equated to 100 However oxidesare artificial forms largely contradicting the actual soil mineralogyFor example the formula of silicon oxide SiO2 corresponds only toquartz while the SiO ratio in aluminosilicate is different 125rather than 12 An analogous situation is observed for aluminumthe formula Al2O3 with an AlO ratio of 1115 corresponds tocorundum which is very rare in soils Aluminum hydroxides(gibbsite Al(OH)3 and boehmite AlOOHwith AlO ratios of 13 and12 respectively) are most common minerals in soils (Sokolovaet al 2005)

As for CaO caustic lime is not present in soils at all In calcareoussoils a significant proportion of Ca enters into the composition ofcalcite CaCO3 where the CaO ratio also differs from 11 Ananalogous situation is observed for MgO In calcareous soils whereCaCO3 concentration reaches 15 (Udvardi et al 2016) the realoxygen content of is appreciably higher and the contents of all ashelements are lower than the calculated values

Sodium oxide is also atypical for soils NaCl in the molecule ofwhich the NaO ratio is 10 rather than 105 frequently forms insaline soils

There is also a disagreement for Fe2O3 This is the chemicalformula of hematite one of the iron minerals When iron sulphides(pyrite FeS2 pyrrhotine FeS etc) are present in the soil theconventional expression of chemical composition in the form ofoxides overestimates the content of oxygen by twofold due to bothFe2O3 and SO3 In badland soils strongly contaminated with ironsulphides the content of S is significantly higher This creates

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imbalances in the proportions of elements errors appear in thedetermination of not only S but also of Fe and O The contents of OFe and S can be refined using Moumlssbauer spectroscopy

Such distortion of mineralogy generally creates errors in chemicalcomposition DS Orlov described this artifact long ago with pyriteas an example if the results of its analysis are expressed in oxidestheir sum is 200 (Orlov 1985) The distortion of oxygen content inthe soil solid phase is the main disadvantage of the expression ofchemical composition in the form of oxides

The exact content of oxygen is important for the geochemicalcharacterization of soils Oxygen reflects the progressive develop-ment of weathering and pedogenesis and the degree of badland soilsdegradation The Clarke value of oxygen in the lithosphere 455(Greenwood amp Earnshaw 1997) can be considered as the criticalvalue An indicative Clarke of oxygen in the soils of the Europeanplain is 491 The content of oxygen in the solid phase of mineralRussian soils is higher it is roughly without correction estimated at48ndash52 (Orlov 1985) The exceedance of oxygen content in soilsover the lithosphere characterizes the development of weatheringand pedogenesis processes The content of oxygen below the Clarke(455) on the contrary reflects the degradation of badland soils

The errors in the determination of oxygen also result in errors inthe contents of other macro-elements in the soil Significant errors inthe total chemical composition of soil are also due to CaO MgOK2O and Na2O because these metals do not generally occur in thesoil as oxides In soils containing iron sulphides the content ofoxygen in soils is overestimated when the contents of Fe and S areexpressed in oxides This results in an error in the determination ofFe and especially S

The aim of this work was to study iron sulphides in badland soilsand to propose a procedure for the correction of their bulkcomposition

Setting

Suburbs of the city of Karabash belong to the South-Uralmountainous landscape province with the dominance of gray anddark gray forest soils The copper-smelting industry radically alteredthe landscape and the soils in the area Anthropogenic pollutionsignificantly affected the soils on Mount Zolotaya to the east of theKarabash copper smelter (Linnik et al 2013)

The Sak-Elga River valley including the Ryzhii Brook which isalmost lacking vegetation because of pyrite waste discharge iscomposed of anthropogenic sulphidendashsilicate material A study ofthe current geo-ecological situation in the vicinity of the Karabashcity was conducted in July 2012 (Linnik et al 2013) Four soilsampling plots were selected in the zone of the anthropogenicbadlands at different distances from the smelter (Fig 1) T1-1250 mT2-1700 m T3-3800 m and T4-750 m They characterize theconditions of geochemical transfer of substances by water flowsalthough under different landscape conditions TheBadlands includedeposits of two types (1) alluvial deposits of the Ryzhii Brook (plotsT1 and T2) and the Sak-Elga River floodplain (plot T3) and (2)deluvial deposits on the lower slope of Mount Zolotaya (plot T4)

All the selected monitoring plots were characterized by almostcomplete elimination of the upper organic soil horizons includinglitter Parent rock occurs directly under the anthropogenic layer

Plot T1 is located at the first large tailing dump which includes57 million tons of pyrite-containing waste rock Soils werecollected on the Ryzhii Brook right bank at 15 m from the brookbed This is poorly sorted coarse-grained sand without clear layeredstructure In the upper part of the pit fragmentary yellow pyritelayers of few millimeters to 1ndash2 cm thick are visible

Plot T2 is selected in the middle part of the Ryzhii Brook basin ina low floodplain on the left bank at 20 m from the brook bed

Fig 1 Location of the four soil samplingplots (T1ndashT4) and the smelter

YN Vodyanitskii et al

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Material is saturated with water alluvial deposits are yellowish-grayin color bottom sediments in the brook bed (15ndash2 m broad) arebright rust-red in color The soil has a clear fine-stratified structureThin pyrite interlayers are visible in the pit

Plot T3 is located at 15 km from the mixing zone of natural waterfrom the Sak-Elga River and wastewater from the Ryzhii BrookSamples from the 0ndash5-cm layer consist of poorly sorted alluviumwith large inclusions of gravel up to 2ndash3 cm in size Alluviummainly consists of ferruginous sand There is no sedimentstratification The composition of alluvial deposits is also affectedby the Novoe tailing dump enriched with pyrite and located on theright bank of the Sak-Elga River valley Tailings are graduallyscoured and extend to the Sak-Elga River (Ulrsquorikh amp Timofeeva2015)

Plot T4 is located on the lower slope of Mount Zolotaya Theslope is covered by stony eluvial-diluvial deposits The soil issimilar to takyr its thin loamy crust up to 1 cm thick breaks intopolygonal blocks under drying The western slope of MountZolotaya is bare (Linnik et al 2013)

Methods

According to FAO (2006) badland samples are classified as SpolicTechnosols The sampling plots were no smaller than 50 times 50 cm insize soil samples were collected from the surface layer to a depth of5 cm by the envelope method

Particle size distribution in samples was determined by thepipette method with the dispersion of aggregates by pyrophosphate(GOST 12536-79 1979)

Mineralogy of soil particles (lt001 mm) was determined bymicroscopy according to Methodological recommendations (2008)which is recommended according to Russian standards

Iron minerals were studied using MS1104Em Nuclear GammaResonant (Moumlssbauer) Spectroscopy with a Co57 (Rh) source in arhodium matrix Model interpretation was performed usingSpectrRelax software (Matsnev amp Rusakov 2012) The isomershifts were calculated with respect to the metallic α-Fe The sampleswere cooled in the helium cryostat ССS-850

The bulk chemical composition of badland samples wasdetermined with two X-ray fluorescence instruments a MAKS-GV Spectroscan and a Bruker M4 TORNADO microspectrometerThey differ in their ability to identify chemical elements and insoftware The Spectroscan determines elements beginning from Naand the microspectrometer begins only at Al ie it provides noinformation on Na and Mg There are also differences in thestandardization of the instruments which are appreciable for thedetermination of Fe and S contents in the same badland samplesFinally the difference in calibration methods should be noted theSpectroscan is calibrated in the mass fractions of element oxides forautomorphic soils and the microspectrometer is calibrated in thefractions of elements ie oxygen-free samples Subsequently werecalculated the microspectrometer data to element oxides

Statistical data analyses

All laboratory tests were performed in triplicate The experimentaldata (means and standard deviations) were statistically treated usingEXEL2016 Differences were considered not significant at values ofP gt 005

Results and discussion

Particle size distribution in badland soils

The content of the soil particles (lt001 mm) in samples from theRyzhii Brook for plots T1 and T2 is identical and is only 25 Thecontent of soil particles (lt001 mm) in sediments of the Sak-Elga

River is similar 27 for plot T3 In alluvial deposits the content offine sand (025ndash005 mm) gradually decreases down the brook toplot T3 from 629 to 408 The content of coarse silt (005ndash001 mm) correspondingly increases when going from plots T1(05) and T2 (33) to plot T3 (274) (Minkina et al 2017)

A radically different particle size distribution of diluvial depositsis observed for plot T4 on the lower slope of Mount Zolotaya Theproportion of soil particles (lt001 mm) reaches 246 whichexceeds its content in alluvial deposits by an order of magnitudeThe sum of medium (1ndash025 mm 97) and coarse (025ndash005 mm 301) sand is 398 which is significantly lower thanin the alluvial deposits The content of coarse silt (001ndash005 mm356) also exceeds the content of the analogous fraction in alluvialdeposits Badland material is significantly heavier than alluvialdeposits

Mineralogy of badland soil samples

In valley soils of the Sak-Elga River and its tributary Ryzhii Brook(sites T1ndashT3) the content of magnetite hematite and magneticspherules is only 50ndash68 (Table 1) In the upper layer of badlandsoil (site T4) the content of anthropogenic magnetite hematite andmagnetic spherules reaches 50 (Table 1)

The content of authigenic iron hydroxides in badland soilsincreases from 41 at site T1 in the issue of the Ryzhii Brook to80ndash83 at sites T2 and T3 in the medium course of the brook andthe Sak-Elga River The minimum content of authigenic ironhydroxides is on the slope of Mount Zolotaya Muscovite-chloritesilicate growths are revealed in small amounts on all landscapepositions Carbonates are almost absent in badland soils

The content of lithogenic mineral garnet at site T4 on the mountslope is significantly higher than in the Ryzhii Brook valley and theSak-Elga River floodplain The content of another lithogenicmineral epidote-zoisite at site T4 is also higher than in soils ofanthropogenic floodplain landscapes The same is true for thecontents of colored mica and amphiboles their contents on the slopeof Mount Zolotaya (T4) are significantly higher than at the area ofmining waste transfer by water The contents of colored mica andamphiboles in sites T1ndashT3 are 10ndash12 and 19ndash26 respectively

The contents of the clay minerals muscovite and biotite are alsomaximum at sites T1ndashT3 and minimum at site T4 On the otherhand the content of pyroxene at sites T1ndashT3 is minimum comparedto site T4

Of greatest importance is information on iron sulphides Thecontent of pyrite plus marcasite in the soil particles (lt001 mm) ofbadland samples (T1ndashT3) reaches 75ndash83 while iron sulphides arealmost absent at site T4 (1) The effect of iron sulphides on bulkchemical composition is obviously maximum in the first threebadland samples

Composition of iron minerals

The Moumlssbauer spectra of badland samples obtained at roomtemperature and 15 degK are shown in Figure 2 and their parametersare given in Table 2

At room temperature the spectrum of sample T1 (Fig 2a)consists of two paramagnetic doublets The isomer shifts of bothdoublets correspond to Fe3+ ions (Menil 1985) The broadened linesof doublet D1 and its quadrupole splitting agree with the parametersof doublets observed in the spectra of iron oxide nanoparticles(Kundig amp Boumlmmel 1966 Moslashrup amp Topsoe 1976 Lastovina et al2016 Chuev et al 2017) The parameters of doublet D2 are similarto those of pyrite (Burgardt amp Seehra 1977 Stevens et al 2002)

Superparamagnetism (Bedanta amp Kleemann 2009) appearing iniron oxide nanoparticles (Neacuteel 1949) leads to the line shapedistortions in theMoumlssbauer spectra (Chuev 2013) and the decrease

Sulphides effect on the measurement of the soil composition

by Michael David Campbell on December 4 2018httpgeealyellcollectionorgDownloaded from

in hyperfine magnetic field value due to magnetization fluctuations(Moslashrup amp Topsoe 1976) For example superparamagnetism in thehematite and goethite nanoparticles lt20 nm in size results in thedisappearance of Zeeman splitting of the Moumlssbauer spectra at roomtemperature (Kundig amp Boumlmmel 1966 Janot et al 1973) TheMoumlssbauer spectra in both cases are the doublets with equalparameters Since most of soil minerals have the particle sizes about20 nm or smaller the identification of the iron oxide phase bymeans of Moumlssbauer spectroscopy at room temperature iscomplicated or impossible Low temperature measurement isrequired to reduce the effect of superparamagnetism on theMoumlssbauer spectrum structure (Murad 2010) At 15 degK theMoumlssbauer spectrum of badland sample T1 represents a superpos-ition of sextet and doublet components (Fig 2a) The sextetcomponent corresponds to hematite and the doublet componentcorresponds to pyrite It was found that 33 of Fe3+ ions areattributed to hematite particles while 67 of Fe3+ ions refer topyrite

The spectrum of sample T2 (Fig 2b) at room temperature consistsof three doublets and a sextet (Table 1) The doublet D1 and sextetS1 are associated with hematite The doublet D2 parameterscorrespond to pyrite The doublet D3 parameters are close to thoseof pyroxene (Stevens et al 2002) The Moumlssbauer spectrummeasured at 15 degK is decomposed into two doublets and a sextetWhen the temperature decreases the doublet D2 transforms to asextet which is due to superparamagnetic properties of hematitenanoparticles Pyrite and pyroxenes undergo no magnetic phasetransition in the temperature range of 15ndash300 degK (Wagner ampWagner 2004) Therefore the corresponding components D2 andD3 are paramagnetic doublets Hematite pyrite and pyroxenescontain 51 46 and only 3 Fe3+ ions respectively

The Moumlssbauer spectrum of sample T3 (Fig 2c) includes thesame components as that of sample T2 The spectrum differs only inthe ratio of component areas In sample T3 the component with thelargest area (79) corresponds to hematite The areas of the pyriteand pyroxene components are 18 and 3 respectively

The Moumlssbauer spectrum of sample T4 (Fig 2d) at roomtemperature consists of six components two sextets and fourdoublets At 15 degK the doublet D2 disappears and the areas ofsextets S1 and S2 increase The isomer shifts of sextets S1 and S2correspond to Fe3+ ions Their values indicate the octahedral oxygensurrounding (Menil 1985 Raevski et al 2012) ie the sextetscould correspond to hematite particles of different sizes The sextetS1 with a higher value of hyperfine magnetic field (H = 528 kOe)corresponds to larger particles In addition Fe3+ ions in goethitealso have an octahedral oxygen surrounding The sextet S1corresponds to hematite the sextet S2 might correspond to hematiteor goethite Both doublets D2 and D3 in the spectrum of sample T4correspond to pyroxenes The parameters of the doublet D4 aresimilar to those of the epidote doublet (Stevens et al 2002)

In this badland sample the mineralogy of iron is most diversefive minerals have been revealed Pyrite containing 42 of totalFe3+ ions is prevailing hematite and goethite together contain 42of Fe3+ pyroxenes and epidotes contain 11 and 5 of Fe3+respectively

Bulk chemical composition and its adjustment

Initial chemical composition

The initial chemical composition is given in Table 3 in the form ofelements the sum of which is c 100 The content of directlyindeterminable oxygen was conventionally calculated as thedifference 100 ndash Σelements

It can be seen (Table 3) that the contents of macro-elementsdetermined with two instruments differ significantly In badlandT

able1

Mineralogyof

badlandsoilsamples

Sam

ple

Terrigenous

minerals

Authigenicminerals

Stable

Interm

ediate

Unstable

Ilmenite

Garnet

Epidote-zoisite

Colored

mica

Amphibole

Muscoviteb

iotite

Magnetitehematite

andmagnetic

spherules

Pyroxene

Iron

hydroxides

Pyritem

arcasite

Carbonates

Sulphates

Muscovite-chlorite

grow

ths

T1

tr

017

020

119

204

319

500

051

408

8280

trtr

102

T2

tr019

020

100

186

464

681

073

830

7499

trtr

134

T3

tr020

031

104

261

309

587

091

800

7699

trtr

098

T4

336

096

1152

240

1248

096

5000

1200

288

112

tr040

096

Traces

YN Vodyanitskii et al

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samples T1 the contents of Si (269 and 275) and Al (53 and65) are comparable but the contents of Fe and S are verydifferent The content of Fe is 197 (with the Spectroscan) and55 (with the microspectrometer) and the content of S is 03 and47 respectively In badland samples T2 the contents of Al (48and 19) and S (12 and 44) differ significantly In badlandsamples T3 appreciable differences are in the contents of Fe (188and 114) and S (10 and 51) In badland samples T4 thecontents of Fe are different (164 and 93)

The reliability of results can be judged from the data on S contentIn all badland soils the Spectroscan gives significantly lower values(03ndash12 S) than the microspectrometer (19ndash51 S)Independent mineralogical data indicate the dominance of pyriteFeS2 a sulphur-enriched mineral This is proof in favor of themicrospectrometer which records a higher enrichment of badlandswith S

Adjustment of total oxygen iron and sulphur contents

Moumlssbauer spectroscopy data allow for the adjustment of oxygeniron and sulphur contents in badland soils containing ironsulphides Note that this is only a partial adjustment of bulk

chemical composition In particular only the content of sulphidesulphur will be adjusted although the dissolution of sulphidesproduces sulphates which are not identified by Moumlssbauerspectroscopy Moumlssbauer spectroscopy data can only removesignificant contradictions in bulk chemical composition based onthe expression of elements in the form of their oxides

The chemical composition could be corrected for only threebadland samples T1ndashT3 In sample T1 iron is distributed betweentwo minerals hematite and pyrite which pose no problem forcorrection Badland samples T2 and T3 contain along withhematite and pyrite small amounts of pyroxenes with only 3 oftotal iron The chemical composition of pyroxenes cannot bedetermined The group of pyroxenes includes a wide range (about20) of minerals with specific chemical compositions Therefore wedid not consider pyroxenes and their share of Fe (3) distributedbetween hematite and pyrite

As for sample T4 it has a very complex iron mineralogy alongwith hematite and pyrite pyroxenes (11) and epidotes (5) arepresent in the sample The group of epidotes as well as pyroxenesincludes a range of minerals with different chemical compositionsIn addition sextet S2 is due to the presence of both hematite andgoethite the proportion of each mineral being unknown The

Fig 2 Moumlssbauer spectra of badland soil samples (a) T1 (b) T2 (c) T3 (d) T4

Sulphides effect on the measurement of the soil composition

by Michael David Campbell on December 4 2018httpgeealyellcollectionorgDownloaded from

complex iron mineralogy deteriorates the adjustment accuracy ofbulk chemical composition Therefore the composition of sampleT4 was not adjusted

The adjustment procedure is based on the recalculation of thecontents of three elements (Fe S O) expressed in the form of oxideswith account for their contents in iron oxide and sulphide The maincondition is to observe the equality of the summary contents of theseelements before and after adjustment Otherwise the main principleof bulk chemical composition ndash the equality of the sum of allelements to 100 ndash is violated

For the soil containing sulphides the condition is

S(Fe2O3 thorn SO3)ini frac14 S(Fethorn Othorn S)cor (1)

The right side of the equation summarizes the elements theproportions of which were determined by Moumlssbauer spectroscopyThese proportions can be expressed as the portions of oxygen andsulphur against iron

For sample T1 by the Spectroscan the proportion of hematite(Fe2O3) Fe in the sample is 0333 (as noted above) and theproportion of oxygen in this oxide is 0300 Thus the correctedcontent of oxygen in the (Fe + O + S)cor system is as follows

O frac14 0333 0300 Fe 0100 Fe

The proportion of pyrite (FeS2) in the sample is 0667 and the SFeratio in pyrite is 05020498 = 1008 Thus the corrected content ofsulphur in the three-element system is as follows

S frac14 0667 1008 Fe frac14 0672 Fe

Therefore the balance of these three elements for sample T1 can bepresented in the numerical form The left side of Eq (1) is as follows

(Table 3)

S(Fe2O3 thorn SO3)ini frac14 S(1967=07thorn 028=04) frac14 S(281thorn 07)

frac14 288

The right side of Eq (1) is as follows

S(Fethorn Othorn S)cor frac14 S(1 Fethorn 01 Fethorn 0672 Fe)frac14 1762 Fe

Equalizing the sides of the equation

288 frac14 1762 FeThus the content of Fe in T1 after the adjustment of the Spectroscandata is as follows

Fe frac14 288=1762 frac14 1634 its former value being 1967

The adjusted content of oxygen in the three-element systemdecreased to 011634 = 163 compared to 885 before theadjustment

The adjusted content of S is

S frac14 0672 1634 frac14 1098 compared to only 028 according

to the Spectroscan data

Adjusted bulk chemical composition of badland soils

Along with the original chemical composition determined by thetwo instruments the contents of Fe S and O obtained after thecorrection using Moumlssbauer spectroscopy data for T1ndashT3 are givenin Table 3 It can be seen that the corrections for the content of Swere significantly lower when the chemical composition wasdetermined with the microspectrometer than with the SpectroscanIn sample T1 the content of S determined with the

Table 2 Moumlssbauer spectral parameters of badland soil samples

Sample T degK Component δ plusmn 002 mms εΔ plusmn 002 mms H plusmn 1 kOe G plusmn 002 mms S plusmn 1 Phase χ2

T1 300 D1 033 078 050 34 hematite 1185D2 031 060 027 66 pyrite

15 S1 049 minus010 489 088 33 hematite 1124D2 040 062 030 67 pyrite

T2 300 D1 035 078 052 38 hematite 1273D2 031 060 029 46 pyriteD3 111 134 030 3 pyroxeneS1 035 minus011 465 137 13 hematite

15 D2 041 062 030 46 pyrite 151D3 130 280 030 3 pyroxeneS1 049 minus008 486 085 51 hematite

T3 300 D1 036 074 054 79 hematite 2321D2 036 048 029 18 pyriteD3 110 252 045 3 pyroxene

14 D2 041 070 065 18 pyrite 3781D3 150 244 039 3 pyroxeneS1 049 minus012 496 044 79 hematite

T4 300 D1 037 096 073 24 hematitegoethite 2023D2 035 056 040 42 pyriteD3 113 270 0278 11 pyroxeneD4 040 206 0398 5 epidoteS1 038 minus010 511 043 4 hematiteS2 039 minus010 484 082 14 hematitegoethite

14 D2 045 060 0603 42 pyrite 1941D3 125 284 0376 11 pyroxeneD4 046 206 0352 5 epidoteS1 047 001 528 0445 7 hematiteS2 048 minus009 494 0789 35 hematitegoethite

δ isomer shift ε quadrupole shift Δ quadrupole splitting for paramagnetic components H hyperfine magnetic field on 57Fe nucleusG line width S area of spectrum components

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Table 3 Bulk chemical composition in of soils determined with a MAKS-GV Spectroscan and a Bruker M4 TORNADO microspectrometer before (1) and after (2) correction ()

Treatment Si Al Fe Ti Ca Mg K Na S Cu O

T1Spectroscan1 2746 plusmn 011 534 plusmn 006 1967 plusmn 008 nd 050 plusmn 0002 078 plusmn 0003 050 plusmn 0003 067 plusmn 0002 028 plusmn 0002 nd 46002 2746 534 1634 nd 050 078 050 067 1098 nd 3862

Microspectrometer1 2687 plusmn 007 648 plusmn 004 547 plusmn 003 061 plusmn 007 149 plusmn 002 nd 436 plusmn 009 nd 475 plusmn 005 012 plusmn 0001 49642 2687 648 1239 061 149 nd 436 nd 833 012 3914

T2Spectroscan1 2816 plusmn 023 483 plusmn 005 1722 plusmn 013 nd 029 plusmn 0001 072 plusmn 0004 067 plusmn 0004 082 plusmn 0002 116 plusmn 001 nd 46552 2816 483 1684 nd 029 072 067 082 798 nd 4011

Microspectrometer1 2934 plusmn 017 187 plusmn 001 1443 plusmn 021 007 plusmn 0003 011 plusmn 0005 nd 051 plusmn 001 nd 444 plusmn 009 022 plusmn 0004 48252 2934 187 1942 007 011 nd 051 nd 921 022 3849

T3Spectroscan1 2302 plusmn 029 772 plusmn 014 1876 plusmn 016 nd 136 plusmn 0002 162 plusmn 004 067 plusmn 0005 059 plusmn 001 096 plusmn 002 nd 44602 2302 772 2036 nd 136 162 067 059 389 nd 4007

Microspectrometer1 2669 plusmn 035 532 plusmn 009 1141 plusmn 017 020 plusmn 0004 141 plusmn 002 nd 070 plusmn 0003 nd 509 plusmn 031 006 plusmn 0003 48592 2669 532 2024 020 141 nd 070 nd 387 006 4098

T4Spectroscan1 2354 plusmn 014 830 plusmn 003 1645 plusmn 012 nd 207 plusmn 004 216 plusmn 150 plusmn 0004 067 plusmn 002 044 plusmn 005 nd 4477

Microspectrometer1 2608 plusmn 037 705 plusmn 008 934 plusmn 010 115 plusmn 002 181 plusmn 013 nd 229 plusmn 001 nd 190 plusmn 0007 122 plusmn 001 4515

Not detected

Sulphides

effecton

themeasurem

entof

thesoil

composition

by Michael D

avid Cam

pbell on Decem

ber 4 2018httpgeealyellcollectionorg

Dow

nloaded from

microspectrometer increased by less than twofold and thatdetermined with the Spectroscan increased almost 40 times InT2 the content of S determined with the microspectrometerincreased less than twofold and that determined with theSpectroscan increased almost 7 times In T3 the content of Sdetermined with the microspectrometer increased less than twofoldand that determined with the Spectroscan increased 4 times Thisconfirms again that the standards used for the microspectrometer arecloser to the matrix of the samples that the standards used for theSpectroscan

The chemical composition determined with the microanalyzerchanged after the correction using the Moumlssbauer spectroscopy dataof Fe compounds The most significant increase in the content of Fe(in 25 times) was observed for sample T1

In the three samples the correction for sulphides decreased thecontent of oxygen by 8ndash10 The total content of oxygen in thesamples decreased to 38ndash41 The lowest content of oxygen(385) is in sample T2 which is the most degraded of the threestudied soils At sites T1 and T2 the soils are less degraded the totalcontent of oxygen is slightly higher at 391ndash410

Conclusions

The XRF determination of bulk chemical composition of sulphide-containing soils causes difficulties XRF analyzers uncalibrated forsulphides strongly underestimate the content of sulphur Suitablycalibrated XRF analyzers provide a higher sulphur content but theobtained bulk chemical compositions of sulphide-containing soilsalso require correction because the concentration of oxygen is notpossible The results expressed as oxides are artificial andcontradict the actual mineralogy of the soils A procedure isproposed for the adjustment of oxygen content in the solid phase ofsulphide-containing soils using Moumlssbauer spectroscopic data onthe content of Fe minerals The total iron sulphur and oxygencontents in soils can be adjusted using simple iron mineralogy Thelow content of oxygen in the solid phase of soils reflects their degreeof degradation The method proposed in our work can be used forthe specification of the total chemical composition of soils andsedimentary rocks containing iron sulphides both lithogenic andpedogenic ones (eg for refining the composition of marshy soils)

Acknowledgements The authors thank Jaume Bech Borras and GwendyHall for their advice comments and reviews

Funding This work was supported by the grant of Russian ScienceFoundation (no 16-14-10217)

Scientific editing by Jaume Bech Borras and Gwendy Hall

Correction notice The author name Stanislav V Kubrin was corrected toStanislav P Kubrin

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Lastovina TA Bugaev AL Kubrin SP Kudryavtsev EA amp Soldatov AV2016 Structural studies of magnetic nanoparticles doped with rare-earthelements Journal of Structural Chemistry 57 1444ndash1449

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by Michael David Campbell on December 4 2018httpgeealyellcollectionorgDownloaded from