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ARTICLE IN PRESSG ModelHEMER-25370; No. of Pages 14

Chemie der Erde xxx (2015) xxx–xxx

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Chemie der Erde

j o ur na l ho mepage: www.elsev ier .de /chemer

eochemical mapping based on geological units: a case study fromhe Marnoso-arenacea formation (Northern Apennines, Italy)

alerio Lancianese ∗, Enrico Dinelli.G.R.G., Università di Bologna, via S.Alberto 163, 48123 Ravenna, Italy

r t i c l e i n f o

rticle history:eceived 2 December 2015ccepted 9 December 2015

eywords:eochemical mappingeochemistrytream sedimentsrovenance-mode factor analysisarnoso-arenacea formationeological membersediment compositionource rock weatheringpennines

a b s t r a c t

Geochemical maps can provide us with much information on geology, earth surface processes and anthro-pogenic pressure and are valuable tools for ore prospecting and land management. Stream sedimentsrepresent an integral of the various possible sources of sediments upstream from the sampling pointtherefore there can be multiple signal sources but generally the prevailing signal source is the onerelated to bedrock geology. Stream sediments collected from active second-order channels includingsingular geological units, were selected in order to determine the geochemical characteristics of eachunit. The aim of this study was to analyze their potential for using them to integrate geological inter-pretation and produce a geologically-oriented geochemical map. From the 770 samples collected for aregional geochemical mapping program, we selected 149 samples whose catchment basin included onlyone of the members recognized within the Marnoso-arenacea formation. This middle–upper Miocene(Langhian–Tortonian) turbiditic unit forms the backbone of the Romagna Apennines and has been sub-divided into 14 members according to age and lithostratigraphic criteria. The results indicate that thereare marked differences in the composition of the members of the Marnoso arenecea formation whichindicate the provenance of the sediment and the palaeogeographic evolution of the units. By means ofunivariate and multivariate statistical analyses (Factor analyzes) two main types of sediment compo-sitions are identified: Tortonian members are characterized by sialic coarse grain-sediments while the
Langhian–Serravallian members are richer in carbonate fraction, slightly enriched in a mafic contribution.This study elaborated the geochemical data from a geological point of view by integrating the informa-tion available in literature to spatially extend the interpretation based on limited site observation as forpetrographic studies. In general, the geochemical map based on a geological unit could be a useful tool
gical
for carrying out the geolo
. Introduction

Since the early 1980’s, the geochemistry of clastic (Bhatia, 1983,985a,b; McLennan and Taylor, 1983; McLennan et al., 1993; Taylornd McLennan, 1985; Roser and Korsch, 1986, 1988; Condie et al.,992; Condie, 1993), lake (Krishnamurthy et al., 1986; Fontes et al.,993; Mullins, 1998; Willemse and Tornqvist, 1999; Last and Smol,001; Jin et al., 2001, 2003; Laird et al., 2003; Rose et al., 2004)nd stream sediments (Swennen and Van der Sluys, 1998; Cannont al., 2004; Ortiz and Roser, 2006a,b; Ranasinghe et al., 2008, 2009;

Please cite this article in press as: Lancianese, V., Dinelli,

case study from the Marnoso-arenacea formation (Northern

http://dx.doi.org/10.1016/j.chemer.2015.12.001

ingh, 2010; Bhuiyan et al., 2011) have been used for evaluating tec-onic setting and provenance studies since the original signature ofhe source remains preserved in the sediments. The chemical com-

∗ Corresponding author.E-mail addresses: [email protected], [email protected]

V. Lancianese).

ttp://dx.doi.org/10.1016/j.chemer.2015.12.001009-2819/© 2015 Elsevier GmbH. All rights reserved.

reconstruction of a complex area.© 2015 Elsevier GmbH. All rights reserved.

position of sediments have been analyzed in various ways: sometrace elements like Cr, Ni and Co, which are enriched in mafic andultramafic rocks and Zr and REEs that indicate the control of heavyminerals such as monazite, zircon and apatite, generally remainimmobile throughout the process of sediment production and areuseful indicators of source region composition (Singh, 2010) both inabsolute concentration and as ratios between elements (Taylor andMcLennan, 1985; McLennan et al., 1993; Condie, 1993). Other prox-ies often considered are: (a) the SiO2/Al2O3 ratio, which suggestsclay matrix control and grain size; (b) Na2O and possibly CaO andSr, if carbonates are missing, which can be controlled by feldsparoccurrences.

Stream sediments are composite samples of the outcroppingrocks and surface material upstream from the sampling point(Levinson, 1974; Meyer et al., 1979; Rose et al., 1979; Darnley,

E., Geochemical mapping based on geological units: aApennines, Italy). Chemie Erde - Geochemistry (2015),

1990; Hale and Plant, 1994), are key characteristics for exploration,mapping and management and are useful for determining back-ground concentrations (Bölviken et al., 1990). Therefore stream

dx.doi.org/10.1016/j.chemer.2015.12.001


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ARTICLE IN PRESSG ModelCHEMER-25370; No. of Pages 14

2 V. Lancianese, E. Dinelli / Chemie der Erde xxx (2015) xxx–xxx

Fig. 1. Geological map of MAF modified from the source available at Servizio Geologico, 2014 Sismico e dei Suoli Regione Emilia Romagna showing the 13 members recognizedby Martelli et al. (1994) and the number of samples selected for each member (lower right insert). The area is part of the catchment of nine rivers (upper right insert): Santerno,S ited

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enio, Lamone, Acerreta–Tramazzo, Montone, Rabbi, Bidente, Savio–Borello. It is limnd Marecchia valley. The MAF (lower left insert) is part of the Umbrian Units betnd Quaternary unit at north-east and Cervarola unit at south-west (from Muzzi M

ediment is one of the best media in provenance studies andor determining tectonic setting (Carranza and Martin, 1997;handrajith et al., 2000; Ohta et al., 2004; Cannon et al., 2004;ingh, 2010; Tripathy et al., 2013). The grain-size fraction selecteday significantly affect the analytical results of the stream sedi-ent samples, since there appear to be higher concentrations ofetals in the fine grain-size fractions (Förstner and Müller, 1974).

n particular some authors (Chandrajith et al., 2000) point out howifferent grain-size fractions (<63 micron, 63–125 micron, 125–177icron or 177–250 micron) contain different levels of transition

lements which are generally absorbed in fine-grained sedimentsenerally decreases in concentrations with the increase in grainize (Das et al., 2006). Some of the major elements (Al2O3, Fe2O3,nO, MgO, CaO, and K2O) increase in the finer sediments while

iO2 increases in coarser samples. Moreover, a strong correlations observed between sediment grain size and total organic matterue to the greater absorption capacity of fine sediments with largeurface areas (Meyers and Eadie, 1993; Meyers and Lallier-vergés,999).

When considering these factors and an area where sedimen-ary rocks with different grain size fractions such as sandstonesnd marls occur and are characterized by various provenance sup-lies, it is essential to use a size fraction that represents a wide




ange of signals, in order to accurately determine the geochemi-al signatures of the study area and limit the effect of factors thatould influence the results such as hydraulic sorting and weather-ng (McLennan, 1989; Nesbitt and Young, 1996; Nesbitt et al., 1996).

to the north-west and to the south-east by two allocthonous units of Sillaro valleyLigurian, Subligurian, Epiligurian units at north-west and south-east, the Pliocenees and Tinterri, 2010).

For example, many authors suggest the potential of <0.200 mmfraction (Rose et al., 1979; Hale and Plant, 1994; Demetriades,2014), which includes the fractions from fine- to medium-grainedbed load material (fine sand-silt-clay).

If an adequate sample density is available, it is possible to high-light the lithological effect of specific geological units (Cocker,1999; Lima et al., 2003; Ohta et al., 2005; Albanese et al., 2007;Breward, 2007) by observing the differences that characterize sev-eral rock types (e.g.,: ultramafic, granitoid and sedimentary). Forthis study a high-density stream sediment sampling and a detailedgeological map were used to investigate the geochemical evolutionwithin each single geological unit which showed a strong correla-tion between geological evolution and geochemical composition.The aim is to show how geological landscape units can represent akey of representation in the geochemical mapping approach: thisis an interesting topic since the geochemical map obtained, basedon the geological unit, could prove to be a useful tool for carryingout the geological reconstruction of a complex area and obtain-ing a clear visualization of the spatial distribution of the chemicalelements.

2. Study area


2.1. Geologic and stratigraphic setting

The study area, which covers approximately 2433 km2, islocated in the Romagna Apennines (Northern Italy). It lies


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ARTICLEHEMER-25370; No. of Pages 14

V. Lancianese, E. Dinelli / Ch

etween 11◦14′13.83′′E and 12◦16′17.17′′E; 44◦17′24.43′′N and3◦38′41.65′′N and is delimited in the northwest and the southeasty two allochthonous units of the Sillaro valley and of the Marecchiaalley (Fig. 1). This regional-scale area, as defined by Reimann et al.2010), includes the northern part of the Marnoso-arenacea for-

ation (MAF), a turbiditic unit deposited in the Tuscan–Umbrianortion of the Inner Periadriatic basin during the Miocene epochCipriani and Malesani, 1963a,b,c; Ricci Lucchi, 1978; Ricci Lucchind Valmori, 1980; Gandolfi et al., 1983). This basin was elongatedn a NW-SE direction in front of the growing Northern Apenninerogenic wedge (Ricci Lucchi, 1978, 1981, 1986). In the Romagnapennines it forms a belt which is 90 km long and 40 km wide, andeaches a thickness of up to 3500 m (Fig. 1).

The MAF was subdivided into 14 members for cartographic pur-oses (Table 1 and Fig. 1), according to litostratigraphic criteriauch as the arenite/pelite ratio, the average thickness of arenaceousevels, composition of arenites and stratigraphic position (Martellit al., 1994). These members may be correlated with those proposedy Mutti et al. (2002) and Ricci Lucchi (1981). According to Ricciucchi, the sedimentary evolution involves two stages or basins:n older inner stage (Langhian to Serravallian) and a younger outertage (Tortonian), which is due to the shift over time of the basinepocenter toward the NE and the progressive closure of the MAF

oredeep. Ricci Lucchi (1981) reported that the change from thenner to the outer stage is marked by an increase in the sand/mudatio and a decrease in the clastic carbonate input. Moreover Ricciucchi (1986) stated that MAF deposits can be subdivided into fourepositional sequences, LS (Langhian–Serravallian) and S (Serraval-

ian) characterizing the inner stage, and T1 (Tortonian 1) and T2Tortonian 2) characterizing the outer stage, each recording thehift of the main depocenter (Fig. 2) towards the foreland (E-NE).ecent studies (Argnani and Ricci Lucchi, 2001; Conti, 2001; Muttit al., 2002; Roveri et al., 2002; Lucente, 2004; Muzzi Magalhaes andinterri, 2010; Tinterri and Muzzi Magalhaes, 2011) have shownhat a structural deformation and sedimentary/tectonic load whichxerted control over basin geometry and facies distribution compli-ated the MAF depositional setting. These considerations have ledo a further sedimentary evolution characterized by three stages:

Langhian/Serravallian inner basin, an upper Serravallian phaseecording the transition between the inner and outer basins and aortonian outer basin.

.2. The Mineralogical composition of fine sediment and the mainetrital inputs and petrofacies

Zuffa (1980) divided the arenites into four groups: (1) noncar-onate extrabasinal, (2) carbonate extrabasinal, (3) noncarbonate

ntrabasinal and (4) carbonate intrabasinal. The first group isomposed of quartz, k-feldspar, plagioclase, acidic volcanics,ntermediate volcanics, basic volcanics, phyllite, chloriteschist, ser-entineschist, serpentinite, argillite, siltstone, chert, micas andther minerals. The second group is divided into two categories:

imestone and dolostone. Glauconite represents the third grouphile the fourth group is composed of intraclasts, fossils andicritic grains. Heavy minerals are extremely relevant for the

omposition of geological members: they commonly include zir-on, tourmalite, rutile, garnet, sphene, orthite, epidote, chloritoid,taurolite, glaucophane, kyanite, horneblende, picotite, monazite,enotime, anatase + brookite.

Sediment compositional variations within the MAF basin areue to three main detrital inputs (Fig. 2 and Table 1) (Ricci Lucchind Valmori, 1980; Gandolfi et al., 1983; Ricci Lucchi and Ori,

Please cite this article in press as: Lancianese, V., Dinelli, E., Geochemical mapping based on geological units: acase study from the Marnoso-arenacea formation (Northern Apennines, Italy). Chemie Erde - Geochemistry (2015),http://dx.doi.org/10.1016/j.chemer.2015.12.001

985; Capozzi et al., 1991; Roveri et al., 2002; Mutti et al., 2003;attin and Zuffa, 2004; Muzzi Magalhaes and Tinterri, 2010): arevalently Alpine input (siliciclastic) is attributed to NW-to-SEowing turbidity currents; other important inputs come from the Ta

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ARTICLE ING ModelCHEMER-25370; No. of Pages 14

4 V. Lancianese, E. Dinelli / Chemie d

Fig. 2. Scheme of the main sediment inputs in the MAF basin (redrawn from Gandolfieti

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t al., 1983; Roveri et al., 2002). LS (Langhian–Serravallian), S (Serravallian), T1 (Tor-onian 1) and T2 (Tortonian 2) indicate the location of four depositional sequencesdentified by Ricci Lucchi (1986).

outh-western area, from the growing Apennine mountain beltnd minor inputs are located in the southern and south-easternargins of the basin which create carbonate (“Colombine”) and

ybrid siliciclastic/carbonatoclastic (“Contessa-like”) turbidity cur-ents flowing in the opposite direction towards the NW. Gandolfit al. (1983) associated these provenances with five petrofaciesAlpine I and II, Apenninic I, II and III): among the main distinc-ive petrographic features of Alpine I and II petrofacies there is-feldspar < plagioclase, the presence of dolomite, serpentine schistnd volcanic lithics and a distinctive heavy mineral associationepidote, glaucophane, kyanite). In contrast Apenninic II and IIIandstones are characterized by K-feldspar > plagioclase, the pres-nce of limestone and siliciclastic sedimentary rock fragments and aifferent heavy mineral association (picotite, monazite + xenotime,ircon). Lastly, K-feldspar < plagioclase, fragments of granite andplite and an epidote–glaucophane–kyanite heavy mineral associ-tion are found in Apenninic I.

. Methods

.1. Sampling methodology and analysis

This is an original study, which was developed over the yearsnd integrated in 2011 when further sampling was carried out byhe authors. The entire database (n = 770) was actually discussedn another paper (Lancianese and Dinelli, 2014) but with differentims. In this paper only the part of the database concerning the areaf the Marnoso-arenacea formation (n = 149) has been used.

From the active channel stream sediments were collected with spade from the central active area of the streambed in order toinimize contamination from any bank slip material at a depth of




–10 cm. Two samples were collected at each spot within the sitend the sediment was sieved in the field using a stainless steel sieveith running water. The fraction <180 �m was separated and col-

ected in a 1,5 l bottle, the solid material was then oven dried at

PRESSer Erde xxx (2015) xxx–xxx

40 ◦C until dryness. 30 g were homogenized and milled in an agatemortar and powder pellets were prepared for the XRF analysis. Theanalyses of 26 major and trace element concentrations (SiO2, TiO2,Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, P2O5, V, Cr, Co, Ni, Cu,Zn, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pb, S) were performed by meansof a wavelength dispersive X-ray fluorescence spectrometry with aPhilips PW1480 spectrometer equipped with a Rh tube at the BiGeaX-Ray Fluorescence Lab. Matrix corrections were applied in the ana-lytical work (Franzini et al., 1972, 1975; Leoni and Saitta, 1976;Leoni et al., 1986). According to the analysis of international refer-ence material (see Table in Supplementary material), the estimatedprecision and accuracy for trace element determination was betterthan 5%, except for the elements at 10 ppm or lower (10–15%). Totalloss on ignition (LOI) was estimated after overnight heating at 950◦

in a muffle furnace.

3.2. Data selection and treatment

The samples of Marnoso-arenacea database (n = 149) wereselected according to specific criteria in order to obtain samplesthat better represent the bedrock signal for each geological mem-ber. In fact, the hydrographical network flows in a SW-NE directionwhile the geological units spread out in a NW-SE direction (Fig. 1),therefore there are several catchment basins that are crossed byvarious geological members. This could lead to the alteration of thegeochemical signal, especially in samples taken from high streamorder. Due to these factors, the samples were selected from lowstream order catchments (Fig. 3a) which only include one geologi-cal member (Fig. 3b). Moreover, this criterion enabled us to excludeareas where the anthropogenic disturbances were clear, in partic-ular in the industrial areas of the valleys located on high streamorder sections. At least two samples were taken for each memberof the MAF (see Fig. 1 and Table 1) although it was not possible toidentify unique samples for MAF6 and MAF7, which were thereforeexcluded from the following elaboration.

The computation of median and median absolute deviation(MAD) and the calculation of the Levene test that determines theequality of the variances of several data groups (Levene, 1960;Brown and Forsythe, 1974) were carried out in R, a free softwareenvironment (http://cran.r-project.org), using the DASplusR pack-age (http://www.statistik.tuwien.ac.at/StatDA/DASplusR/) as wellas the Factor Analysis (FA) in order to describe the data in terms ofcorrelation structures that fit a predefined number of components(factors) and for processing the notched boxplot of chemical ele-ments. Binary diagrams of elemental ratios were constructed withthe GCDkit package (Janousek et al., 2006).

3.3. Methodology for the elaboration of geochemical maps

In this paper, we consider a geologically complex study area sup-ported by high-density sampling and detailed geological landscapeunits. According to the availability of a detailed 1:10000 geologi-cal map of the area from the “Servizio Geologico, 2014 Sismico edei Suoli” of the Emilia Romagna region providing a background ofsuitable resolution, the geochemical maps were drawn up usingthe geological members of MAF as landscape units. Each mem-ber was assigned the median element concentration of the streamsediments collected within the unit. The median values of the geo-logical members, represented in a summary boxplot, were thensubdivided in accordance with the 25th, 50th, 75th and 90th per-


centiles for mapping purposes the same filling was then appliedto the whole member area. The geochemical maps were producedwith the Quantum GIS, geographic information system software(http://www.qgis.org/).


http://cran.r-project.org





http://www.statistik.tuwien.ac.at/StatDA/DASplusR/









http://www.qgis.org/






V. Lancianese, E. Dinelli / Chemie der Erde xxx (2015) xxx–xxx 5

Fig. 3. Scheme of the criteria used for the stream sediment samples selection. The figure reflect the sampling applied in the complete geochemical mapping project withsampling high order and low order with selected open dots indicate samples representative of single catchment. The final criteria is displaying the b which indicates thatsample selected for the detailed geochemical discussion where only those included in a single lithological unit. Stream sediments were collected with specific criteria ino r (blaa cludid

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rder to avoid contamination sources: (a) samples collected from high stream ordectivities and influenced by multiple sources; (b) samples collected in catchment inifferent geochemical signals.

. Results and discussion

.1. Stream sediment composition

Table 2 reports the statistical parameters (median and medianbsolute deviation (MAD)) for the members of the MAF. Selectedajor and trace element variations as well as geochemical ratios

re presented as box-plots in Fig. 4.Considering the major elements (Fig. 4), the median con-

ent of Al2O3 increased from MAF1 (9.5 ± 1.87 wt.%) to MAF1411.1 ± 0.45 wt.%) while the value of CaO decreased fromanghian–Serravallian (25 ± 5.7 wt.%) to Tortonian members13 ± 2.5 wt.%). MgO, Na2O, and SiO2 values were higher inortonian members: in particular the median content of SiO2

ncreased constantly from MAF1 (30 ± 7.1 wt.%) to MAF1450 ± 6.5 wt.%) while discontinuous values were observed forhe MgO and Na2O concentrations although they showed sim-lar trends to SiO2. The median content of Mg increased fromanghian–Serravallian (3.1 ± 0.55 wt.%) to Tortonian members3.9 ± 0.13 wt.%) with a peak in MAF10 (4.3 ± 0.95 wt.%) while the

edian content of Na2O increased from MAF1 (0.61 ± 0.25 wt.%)o MAF14 (1.38 ± 0.22 wt.%). Fe2O3/Al2O3 and MgO/Al2O3 ratioslso showed significant differences: Fe2O3/Al2O3 ratio presentedower values in Tortonian members (0.33–0.39) compared toanghian–Serravallian members (0.40–0.42) while the MgO/Al2O3atio was lower for Langhian–Serravallian members (0.35–0.36)han for Tortonian members (0.37–0.39) with some exceptionsMAF8, MAF13, MAF14). Trace elements concentrations showedimilar trends (Fig. 4): fundamentally Nb, Rb, V, Zr, Y and Cencreased from MAF1 to MAF14. Sr followed the same evolution ofaO, it therefore decreased from MAF1 (608 ± 121 ppm) to MAF14




305 ± 66 ppm).In general the results showed a lithologic control that may be

ue to major provenance inputs and grain-size balance betweenandstones and marls (A/P ratio), which is a discriminating

ck dots) have been deleted because are located near sites characterized by humanng different geological members (black dots) are deleted because contaminated by

member attribution (see Table 1). The high SiO2 values of the Tor-tonian members (MAF10 = 43 ± 5.4 wt.%; MAF11 = 45 ± 8.4 wt.%;MAF12 = 45 ± 5.9 wt.%; MAF13 = 48 ± 3.7 wt.%;MAF14 = 50 ± 6.5 wt.%) indicate a greater amount of coarsegrained material of sandstones that the finer grained material ofmarls and their importance as indicators of Alpine provenance, assuggested by the studies carried out by Ricci Lucchi and Valmori(1980), Gandolfi et al. (1983), Ricci Lucchi and Ori (1985), Capozziet al. (1991) and Roveri et al. (2002). The same considerationsmight also explain the high Na2O and Rb results in these membersas they are correlated to the higher proportions of plagioclase andfeldspar, which are known to be abundant in this section of the MAF(Gandolfi et al., 1983; Cavazza and Gandolfi, 1992; Gandolfi et al.,2007). The high CaO and Sr concentration in Langhian–Serravallianmembers could indicate the major importance of limestone clasticinputs which are deemed to come from Apenninic sources (RicciLucchi and Pialli, 1973 ; Ricci Lucchi and Valmori, 1980 ; Zuffa,1980; Gandolfi et al., 1983; Martelli et al., 1994). Their distributionagrees with the petrographic information available and also pos-sibly indicates the carbonate fraction of marls since their maximaare associated to units with low A/P ratio. Other minor sourcescould be represented by carbonate cement within sandstones ortravertine formation locally observed close to springs or in rifflesbut their contribution cannot be directly assessed. The high MgOvalues in Northeastern members (from MAF10 to MAF14) indicatethe importance and extent of a dolomitic contribution, which wasobserved in the upper portion of the FMA formation (Gandolfi et al.,1983) and attributed to a Southern Alpine source. Although withrestricted range, the MgO/Al2O3 ratio also showed an increase inTortonian members. The decreasing Fe2O3/Al2O3 ratio value fromMAF1 to MAF14 indicates changes in provenance (e.g.,: sources


from acidic rocks?) as well as changes in the sandstone/peliteratio, which if the sandstone is arkosic could maintain high Al2O3.Zr, Y, Ce, in sandstones are generally associated to relativelycommon heavy minerals (e.g., monazite, xenotime, zircon, garnet)


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Table 2Median composition and median absolute deviation (MAD) of 30 chemical elements in MAF geological members.

Element Unit MAF1 (17) MAF2 (10) MAF3 (9) MAF4 (27) MAF5 (17) MAF8 (9) MAF9 (17) MAF10 (7) MAF11 (5) MAF12 (27) MAF13 (2) MAF14 (2)

Median MAD Median MAD Median MAD Median MAD Median MAD Median MAD Median MAD Median MAD Median MAD Median MAD Median MAD Median MAD

Al2O3 wt.% 9.54 1.87 9.12 1 8.22 0.61 9.59 1.01 9.55 0.83 10.79 3.8 9.97 1.48 11.05 2.18 10.6 0.85 11.35 1.3 12.68 0.51 11.1 0.45CaO wt.% 25 5.7 24 4.8 25 5.4 21 4.3 23 3.2 20 9.8 21 3.7 16 1.73 15 1.76 14 2.06 12 0.56 13 2.54Fe2O3 wt.% 3.9 0.71 3.6 0.35 3.4 0.25 3.8 0.4 4.0 0.34 4.2 1.16 4.1 0.58 4.2 0.13 4 0.59 4.3 0.58 4.2 0.46 4.2 0.30K2O wt.% 1.66 0.34 1.56 0.13 1.5 0.24 1.71 0.16 1.62 0.19 1.85 0.59 1.75 0.16 2.05 0.31 1.96 0.16 1.95 0.24 2.2 0.06 1.91 0.10MgO wt.% 3.1 0.55 3.0 0.53 3.2 0.53 3.1 0.43 3.4 0.33 3.7 0.76 3.5 0.37 4.3 0.95 4.3 0.24 4.2 0.25 4.2 0.01 3.9 0.13MnO wt.% 0.12 0.01 0.11 0.01 0.11 0.01 0.12 0.01 0.11 0.01 0.11 0.01 0.11 0.01 0.12 0.01 0.12 0.01 0.13 0.01 0.16 0.02 0.14 0.01Na2O wt.% 0.61 0.25 0.79 0.08 0.72 0.31 0.69 0.415 0.77 0.21 0.5 0.13 0.82 0.22 0.76 0.13 0.81 0.19 1.03 0.22 1.41 0.22 1.38 0.22P2O5 wt.% 0.1 0.07 0.11 0.04 0.08 0.07 0.12 0.03 0.1 0.03 0.11 0.05 0.1 0.03 0.12 0.03 0.16 0.01 0.14 0.07 0.1 0.01 0.16 0.06SiO2 wt.% 30 7.1 31 7.0 31 7.8 36 4.9 34 4.1 38 5.0 36 4.7 43 5.4 45 8.2 45 5.9 48 3.7 50 6.5TiO2 wt.% 0.48 0.06 0.42 0.04 0.4 0.04 0.46 0.04 0.42 0.04 0.51 0.13 0.46 0.04 0.55 0.74 0.54 0.06 0.56 0.07 0.56 0.01 0.66 0.16Fe2O3/Al2O3 0.42 0.04 0.40 0.01 0.40 0.03 0.41 0.03 0.40 0.04 0.41 0.02 0.39 0.02 0.39 0.03 0.39 0.02 0.36 0.03 0.33 0.02 0.38 0.01MgO/Al2O3 0.349 0.03 0.35 0.05 0.348 0.06 0.337 0.04 0.36 0.03 0.346 0.01 0.371 0.07 0.375 0.09 0.392 0.04 0.353 0.05 0.33 0.01 0.35 0.00Ba ppm 271 58 289 40 309 37 290 34 300 42 306 21 305 45 319 45 304 7.4 334 42 375 39 338 79Ce ppm 44 10.2 35 14 42 12 44 12 40 12 48 12 41 10 50 5.9 54 4.5 55 8.8 50 9.0 64 4Co ppm 7.8 4.2 5.7 2.97 6.1 2.97 7.3 2.5 9 2.97 8 4.5 8 2.97 9 2.97 9 0.07 10 2.97 10 2.52 8.9 1.33Cr ppm 90 19 87 13 75 18 81 15 94 8.9 88 22 91 8.2 97 8.9 92 19 99 18 104 8.4 97 12.1Cu ppm 31 6.1 25 5.2 26 5.3 27 4.5 27 5.9 35 5.9 27 2.97 29 5.9 24 5.9 29 7.4 18 9.0 26 3.3La ppm 25 5.0 19 5.2 15 9.5 22 4.5 21 4.7 24 2.22 23 5.8 25 4.5 26 1.48 28 6.4 26 11 29 2.89Nb ppm 6.2 1.19 7 1.19 6.3 0.74 7 1.48 8 1.78 10 2.97 7.4 1.48 10 4.5 10 1.48 9 4.5 7.3 0.22 52 67Ni ppm 63 11.9 61 5.4 59 4.2 55 8.9 65 7.4 51 12 62 7.7 65 7.4 51 8.9 57 14 56 13 49 13Pb ppm 7.9 5.8 11 5.8 7.6 3.3 13 3.1 8 3.0 12 5.3 8.1 4.6 17 2.97 20 1.48 15 7.3 11 1.19 16 1.04Rb ppm 78 12 75 16 78 13 77 12 79 15 92 31 84 11 101 25 83 12 86 22 98 22 95 17S ppm 931 458 770 111 1150 312 770 362 690 400 1000 104 1110 382 630 297 530 222 870 769 840 901 1213 835Sr ppm 608 121 561 47 420 101 471 128 531 37 437 73 480 200 290 76 269 27 275 41 229 48 305 66V ppm 71 11 64 9.0 64 12 61 9.3 68 5.9 69 17 74 7.1 72 5.9 71 8.9 79 11 84 8.1 69 1.63Y ppm 14 3.0 16 1.78 12 2.1 18 3.0 17 6.7 20 7.9 17 3.7 25 4.5 25 3.0 24 7.4 20 5.1 29 14Zn ppm 82 28 61 11 78 13 65 10 65 13 68 13 96 19 72 8.9 67 12 76 25 75 25 81 25Zr ppm 72 59 83 54 68 54 106 26 87 31 100 30 95 41 158 15 170 43 179 106 126 5.1 232 177




Fig. 4. Box-plots showing the variations of selected major elements (Al2O3, CaO, SiO2, MgO), geochemical ratios (Fe2O3/Al2O3, MgO/Al2O3) and selected trace elements( o 14)

T e elem( ision

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Rb, Sr, Ce, Nb, Y) in geological members of MAF. The numbers in Y axis (from 1 the values in X axis are expressed in wt.% for major elements and ppm for tracLS = Langhian–Serravallian; ST = Serravallian–Tortonian; T = Tortonian) based on div

n the FMA (Gandolfi et al., 1983) and could be useful additionalrovenance indicators. However their interpretation may bembiguous as sorting effects could influence their occurrence inhe alluvial environment where enrichment may indicate a highnergy environment and not source area characteristics (Vital andtattegger, 2000; Dypvik and Harris, 2001; Fralick and Kronberg,997; Garcia et al., 2004; Dinelli et al., 2007) which may occur ifamples are taken from highly sloping streambeds.

Geochemical maps of MAF based on geological members asartographic units could be useful tools for understanding theeological history of the area. Some clear relationships betweenhemical element content and geological stages can be seen inhe geochemical maps in Fig. 5. For example Fig. 5a and Fig. 5chows higher levels of Al2O3 and SiO2 along the north-easternart of the area corresponding to the Tortonian stage while Fig. 5bhows a higher median concentration of CaO along the south-estern part corresponding to Langhian–Serravallian members.

hese maps show the nature of the provenance of turbidity cur-ents deposited in the FMA foredeep: the sialic coarse-grainedurbidity current from the north-eastern Alpine area and thearbonate-rich fine-grained turbidity currents originating frompenninic sources. Fig. 5d shows a larger content of MgO in theortonian members, which confirm the dolomitic contributionf this stage, but also in the Apenninic contribution that char-




cterizes the Langhian–Serravallian stage. Fig. 5e clearly showshe higher amount of Na2O contained in the geological mem-ers of the Tortonian stage suggesting that they are significantlyffected by minerals such as plagioclase. Considering element

indicate geological members from MAF1 to MAF14 (excluding MAF6 and MAF7).ents. The box-plots have been subdivided in three chronostratigraphic periods

shown in Table 1, in order to highlight differences in the evolutionary trend of MAF.

ratios, Fig. 5f shows the highest Fe2O3/Al2O3 values in the high-carbonate members of Langhian–Serravallian stage suggesting thepossible presence of a slightly higher mafic supply in sedimentsdeposited during this period or the presence of iron-rich clay min-erals. In Fig. 5g the highest values of the MgO/Al2O3 ratio areobserved in the central area, possibly indicating a less evident, yetpresent, dolomite contribution also observed also in other prove-nances (Gandolfi et al., 1983): for example the dolomite alpinesupply that characterizes the Tortonian members does not appearclearly in this figure due to the high levels of Al2O3 attributed tothe plagioclase content.

Some important graphical results are also provided by the traceelements: Rb and Sr have opposite distributions as they are ele-ments respectively related to the sialic and carbonatic componentsof the sediment (Fig. 5h and i). In these figures the sialic compo-sition of Tortonian members characterized by a higher content ofRb and the carbonate composition of Langhian–Serravallian mem-bers characterized by higher levels of Sr can be clearly identified.The distribution of Ce, Nb and Y (Fig. 5l–n) highlight higher valuesin the Tortonian members whose turbidity currents were richer inheavy minerals (Gandolfi et al., 1983).

4.2. Geochemical signatures


A more general indication can be obtained by applying the factoranalysis to the selected data set. The analyzes included the 28 ele-ments listed in Table 2, excluding As and Ga since many sampleswere below the detection limit. The results of the factor analysis




F Al2O3

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ig. 5. Geochemical maps of Al2O3 (a), CaO (b), SiO2 (c), MgO (d), Na2O (e), Fe2O3/teps: the median values of geological members of MAF have been extracted and caeen assigned to each geological members considered such as landscape units.

ndicate 5 factors with eigenvalues >1, accounting for 77% of theotal variance, which are discussed in detail and shown in Table 3.

The first factor (positive Al2O3, Co, Cr, Fe2O3, MgO, K2O, Ni, Rb,; negative CaO) explaining 43% of the total variance (Table 3)an be mainly attributed to the clayey fraction of the sediment,hich is opposed to a carbonate fraction. There is a significant

lay mineral fraction in the type of samples analyzed, based on aelatively fine-grained fraction. The stratigraphic distribution out-ined by factor scores (Fig. 6) showed a slight increase in higher

edian values from Serravallian (lowest median value revealedn FMA4 = −0,45) to Tortonian members (highest median valueevealed in FMA13 = 0,89), although the values are irregular. Thisrend is also evident in the statistical difference between the vari-nces of Tortonian members and Langhian Serravallian members




bserved by means of Levene’s test (F value = 0.01). There is lit-le information on the mineralogy of the fine-grained fraction ofhe MAF (Talling et al., 2007) indicating that the mudstones orig-

(f), MgO/Al2O3 (g), Rb (h), Sr (i), Ce (l), Nb (m), Y (n) have been carried out in twoed in a class division based on 25◦ , 50◦ , 75◦ and 90◦ percentile; median values have

inating from north-western sources (Alpine) are enriched in illiteand mica and to a lesser degree in dolomite, while the beds orig-inating from the southeast and the southwest (Apenninic) have asignificantly higher carbonate content and slightly higher quartzcontent. The geochemical map of the first factor (Fig. 7a) showsan increasing content of clayey component in Tortonian membersand also high levels in Langhian–Serravallian members, especiallyFMA5 and FMA8.

The second factor, explaining 16% of the total variance, is char-acterized by high positive loadings of Ce, La, P2O5, SiO2, TiO2, Y, Zrand negative loadings of CaO and Sr (Table 3). The elements withpositive loadings could be attributed to a set of heavy minerals thatare present in the sediment and derive from the outcropping rocks.The presence of SiO2 could be due to the occurrence of quartz and


may be associated with a fine-sand coarse silt sediment fraction(Dinelli et al., 2006) possibly enriched in steep sloping channels. Asalready mentioned, a similar geochemical association was observed




F geologc ave bS rder to

ime(F

ig. 6. Box-plots showing the variations of factor scores (F1, F2, F3, F4, F5) in

al members from MAF1 to MAF14 (excluding MAF6 and MAF7). The box-plot hT = Serravallian–Tortonian; T = Tortonian) based on division shown in Table 1, in o

n sediments and sedimentary rocks from high-energy environ-ents (Fralick and Kronberg, 1997; Dypvik and Harris, 2001; Garcia




t al., 2004). The stratigraphic pattern outlined by factor scoresFig. 6) indicates a shift towards higher median values from olderMA members towards younger members and can be seen in the

ical members of MAF. The numbers in Y axis (from 1 to 14) indicate geologi-een subdivided in three chronostratigraphic periods (LS = Langhian–Serravallian;

highlight differences in the evolutionary trend of MAF.

geochemical map (Fig. 7b). The youngest members outcrop in theclosing section of the Santerno and Savio rivers (Fig. 1), which are


areas characterised by lower topographic gradient compared to theother sampling sites in the upper reaches where older membersoccur. Of course localized situations advantageous for heavy min-




Fig. 7. Geochemical maps of F1 (a)

Table 3Table of factor loadings.

Chemical element F1 F2 F3 F4 F5

Al2O3 0.878 0.272 0.338Ba 0.401 −0.160 0.456CaO −0.663 −0.387 -0.607Ce 0.332 0.701 −0.127 0.189 0.102Co 0.778 0.228 0.111 0.267Cr 0.645 0.358 0.601Cu 0.245 −0.146 −0.456Fe2O3 0.837 0.437 0.137K2O 0.868 0.196 0.340La 0.306 0.702 0.123MgO 0.580 0.270 0.204 0.340MnO 0.271 0.451 −0.249Na2O 0.131 0.319 −0.267 0.792Nb 0.410 0.139 0.175Ni 0.479 −0.201 −0.147 −0.203 0.738P2O5 0.220 0.555 0.605 0.138Pb 0.150 0.211 0.694 0.175 −0.147Rb 0.713S −0.165 −0.109 -0.536Sc −0.190 0.847 −0.334SiO2 0.461 0.448 0.252 0.706Sr −0.411 −0.301 −0.618 0.109Th 0.174 −0.832TiO2 0.363 0.873 0.197V 0.896 0.250 −0.141 0.147Y 0.193 0.794 0.393 0.189Zn 0.499 −0.508Zr 0.791 0.432 0.344

SS loadings 7.045 4.974 3.558 3.074 1.222

ete

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4.3. Different supplies of material: the evolutionary trend of MAF

Proportion of variance 0.252 0.178 0.127 0.110 0.044Cumulative proportion 0.252 0.429 0.556 0.666 0.710

ral accumulation can occur, but this consideration is more likelyo be related to the bedrock composition rather than the sortingffect.

The third factor explains 8% of the total variance and includeshe positive Al2O3, Ba, Na2O, K2O, Si2O and the negative CaO andr (Table 3) values that can be attributed to a relatively coarse-rained fraction dominated by feldspars and plagioclase whichs opposed to a carbonate fraction, possibly also associated to aoarse-grained fraction. The stratigraphic distribution outlined byhe factor scores (Fig. 6) indicates an increase in median values




rom Langhian–Serravallian to Tortonian members which confirmshe arenite/pelite ratio trend shown in Table 1. The geochemical

ap of the third factor (Fig. 7c) clearly shows that the plagio-

, F2 (b), F3 (c), F4 (d), F5 (e).

clase component increases in Tortonian members thus confirminghow the Alpine turbidites deposited in the foredeep followingLanghian–Serravallian have been essential for determining the sed-iment composition of these geological members.

The fourth factor explains 6% of total variance. It includesPb–P2O5–Y–Zr–Si2O and negative Zn–S (Table 3) values which maybe related to a heavy mineral and relatively coarse-grained frac-tion and may indicate possible anthropogenic inputs, controlledby organic matter occurrences that affect the phosphorus con-centrations, as suggested by Lancianese and Dinelli (2014). Thestratigraphic plot outlined by factor scores (Fig. 6) shows an irreg-ular trend characterized by a slight increase of the median valuesfrom Langhian–Serravallian members to Tortonian members andcomplicated by some exceptions (MAF4, MAF9, MAF12, MAF 13and MAF14). This trend is less evident than the F1 trend; in factthe statistical difference between the variances of Tortonian mem-bers and Langhian–Serravallian members outlined by Levene’s testis less robust (f value = 0.3). This trend is only barely visible butit is in line with the expected results: the higher F4 values inTortonian members explain the enrichment of Pb in typical min-erals (feldspars, mica, zircon and some heavy minerals such asgarnet, epidote, zircon, monazite + xenotime, sphene and stauro-lite) and rock sources (granites, shales) of these members (Fig. 7d).The lower F4 median values in Langhian–Serravallian members areaffected by the supply of carbonate and limestone to the geologicalmembers. The only exception, represented by the high F4 value inMAF4, may be due to the anthropogenic inputs that characterizethe strong Pb–P2O5 association; indeed MAF4 is distributed alongsome valleys (Montone, Acerreta-Tramazzo, Lamone and Senio) inwhich there are contaminated sites and widespread anthropogenicinfluence (Lancianese and Dinelli, 2014). The difference betweenSerravallian–Tortonian members (MAF8 and MAF9) is due to theirhybrid composition.

The fifth factor explains 4% of total variance including Cu–Zn andnegative Na2O (Table 3) as observed for the previous factor, thereare no significant differences among the members (Fig. 6) thereforea lithologic control can be excluded. The positive elements probablyindicate a signal of widespread pollution, which was not entirelyremoved during the selection step.


The components highlighted in factor scores can be investigatedusing variations of element ratios in binary plots. Considering the


Please cite this article in press as: Lancianese, V., Dinelli, E., Geochemical mapping based on geological units: acase study from the Marnoso-arenacea formation (Northern Apennines, Italy). Chemie Erde - Geochemistry (2015),http://dx.doi.org/10.1016/j.chemer.2015.12.001



Fig. 8. Binary plot of CaO/Al2O3 vs. Rb/Sr showing the distribution of MAF geological members. The sources for the reference rocks: ultramafic rocks (Turekian and Wedepohl,1961; Puchelt, 1992), metamorphic rocks (Wedepohl, 1995), igneous rocks (Morgan et al., 1978) greywackes (Wedepohl, 1995), marine shales (Li, 1991), granites (Le Maitre,1976), marine pelagic clay (Li, 1991), North American Shale Composite (NASC) (Morgan et al., 1978; Li, 1991), peridotites (Le Maitre, 1976), ophiolitic gabbros (McDonough,1991), Northern Apennines sandstones (Macigno formation, Modino sandstones, Cervarola Sandstones, Marnoso-arenacea formation, from Dinelli et al., 1999) and limestones(Reimann and de Caritat, 1998).

Fig. 9. Binary plot of Cr/V vs. Y/Ni (Hiscott, 1984) showing the distribution of MAF geological members. Element contents of rocks used as references (metamorphic rocks,greywackes, marine shales, granites, marine pelagic clay) are from Morgan et al., 1978; Wedepohl, 1995 and Li, 1991. Element contents of Northern Apennines sandstones(Cervarola, Macigno, Modino and Marnoso-arenacea formation) and ultramafic rocks are from Turekian and Wedepohl (1961) and Puchelt (1992).


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resence of sialic, carbonatic, mafic and heavy mineral components, division of MAF members related to their provenance and com-osition may be deduced. With the aim of distinguishing possible

nputs, average data representing important rock types and localources were included as references in Fig. 8 and 9.

In order to evaluate the silicate and carbonate supplies ab/Sr vs. CaO/Al2O3 diagram was used (Fig. 8), considering theselements as rough indicators of the variations in the siliclas-ic/carbonate ratios. The predominant siliciclastic source inputsave high Rb/Sr and low CaO/Al2O3 ratios while carbonatic inputsave low Rb/Sr and high CaO/Al2O3 ratios. The separation in theeological members of MAF shows a significant variation over timen the two types of contribution: the carbonate inputs characterizehe Langhian–Serravallian stage while siliciclastic inputs affect theortonian stage. In fact considering the references and the resultslready presented, there is a clear evolutionary trend showing aecrease in carbonate inputs from Langhian–Serravallian mem-ers to Tortonian members. Moreover the members deposited

n the Upper Serravallian–Lower Tortonian (MAF8, MAF9) showeochemical features belonging to both Tortonian and Langhianerravallian members: this dispersion could be attributed to theontemporary deposition of siliciclastic and carbonate detritusnputs which occurred during this period (Ricci Lucchi and Valmori,980; Gandolfi et al., 1983; Ricci Lucchi and Ori, 1985; Capozzi et al.,991; Roveri et al., 2002).

The mafic and felsic supply was determined by means of a Y/Nis. Cr/V diagram (Hiscott, 1984). In Fig. 9 the Langhian–Serravallianembers (MAF1–MAF5) tend to have a slightly higher Cr/V ratio

han most of the other samples, while the Tortonian membersMAF-10-14) have a much higher Y/Ni ratio which indicates a sialicupply. In this graph the members deposited in Serravallian sup.-ortonian inf. (MAF8, MAF9) are positioned between Tortoniannd Langhian–Serravallian members indicating a mixed supply.y comparing this graph to a similar graph presented in Dinellit al. (1999) whose samples were represented by another sam-ling media (sandstones rather than stream sediments), a decrease

s observed in the Y/Ni values, highlighted by the boxplots of the-axis (Fig. 9), which shows the increasing influence of fine-grainedediments, as suggested by the position of the reference data.

. Conclusions

The results of this study show that the distribution pattern ofhemical elements is greatly influenced by geological members.fter carefully selecting samples that represent each single geolog-

cal member, in accordance with cartographic information, theseata can be used for extending the interpretation over a widebasin) area. By referring to the data analyses and the geochemical

aps produced and considering the time-dependent evolutionaryrend of geological members from Langhian to Tortonian stage, theollowing conclusions can be made:

) In the Langhian–Serravallian inner stage, south-western geo-logical members (from MAF1 to MAF5) are characterized byprevailing carbonate, fine-grained sediments deriving fromsouthern Apenninic supply.

) In the Serravallian–Tortonian stage, considered as the phase oftransition between the inner and outer stages, geological mem-bers as MAF8 and MAF9 have hybrid geochemical features sincethey are influenced by both Appenninic and Alpinic turbiditycurrents characterized by a decrease in the carbonate signal and




an increase in the siliciclastic contribution.) In the Tortonian outer stage, the north-eastern geological

members (from MAF10 to MAF14) are characterized by sialic,siliciclastic (either enriched in plagioclase and mica) with high


MgO related to significant dolomite inputs deriving from Alpinesupply.

These considerations are in agreement with available petro-graphical, mineralogical and geochemical literature. One of themain differences is that previous reconstructions were based onpoint observation while these data cover a large part of the outcroparea on the MAF in order to obtain a wider overview. The selectionof appropriate data and the availability of high quality supportinginformation enabled us to determine a chronological evolutionarytrend in the deposits of MAF and their distribution is clearly shownin the geologically oriented geochemical maps.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, inthe online version, at http://dx.doi.org/10.1016/j.chemer.2015.12.001.

References

Albanese, S., De Vivo, B., Lima, A., Cicchella, D., 2007. Geochemical background andbaseline values of toxic elements in stream sediments of Campania region(Italy). J. Geochem. Explor. 93, 21–34.

Argnani, A., Ricci Lucchi, F., 2001. Tertiary silicoclastic turbidite systems on thenorthern Apennines. In: Vai, G.B., Martini, I.P. (Eds.), Anatomy of An Orogen:The Apennines and Adjacent Mediterranean Basins. Kluwer AcademicPublichers, Dordrecht-Boston-London, pp. 327–350.

Benini A., Cremonini G., Martelli L., 2009a. Note illustrative della Carta Geologicad’Italia alla scala 1:50.000, Foglio 255Cesena. ISPRA-Servizio Geologico d’Italia.

Benini, A., De nardo, M.T., Severi, P., 2009b. Note illustrative della Carta Geologicad’Italia alla scala 1:50.000, Foglio 238Castel S. Pietro Terme. ISPRA-ServizioGeologico d’Italia. Regione Emilia Romagna.

Bhatia, M.R., 1983. Plate tectonics and geochemical composition of sandstones.Geology 91, 611–627.

Bhatia, M.R., 1985a. Composition and classification of Paleozoic flysch mudrocks ofeastern Australia: implication in provenance and tectonic setting interaction.Sediment. Geol. 41, 249–268.

Bhatia, M.R., 1985b. Rare earth elements geochemistry of Australian Paleozoicgraywackes and mudrocks: provenance and tectonic control. Sediment. Geol.45, 97–113.

Bhuiyan, M.A.H., Rahman, M.J.J., Dampare, S.B., Suzuki, S., 2011. Provenance,tectonics and source weathering of modern fluvial sediments of theBrahmaputra–Jamuna river, Bangladesh: inference from geochemistry. J.Geochem. Explor. 111, 113–137.

Bölviken, B., Kellerud, G., Loucks, R.R., 1990. Geochemical and metallogenicprovinces: a discussion initiated by results from geochemical mapping acrossnorthern Fennoscandia. J. Geochem. Explor. 39, 49–90.

Breward, N., 2007. Arsenic and presumed resistate trace element geochemistry ofthe Lincolnshire (UK) sedimentary ironstones, as revealed by a regionalgeochemical survey using soil, water and stream sediment sampling. Appl.Geochem. 22, 1970–1993.

Brown, M.B., Forsythe, A.B., 1974. Robust tests of the equality of variance. J. Am.Stat. Asso. 69, 364–367.

Cannon, W.F., Woodruff, L.G., Pimley, S., 2004. Some statistical relationshipsbetween stream sediment and soil geochemistry in northwesternWisconsin—can stream sediment compositions be used to predict compositionof soils in glaciated terranes? J. Geochem. Explor. 81, 29–46.

Capozzi, R., Landuzzi, A., Negri, A., Vai, G.B., 1991. Stili deformativi ed evoluzionetettonica della successione Neogenica Romagnola. Studi Geol. Camerti 1,261–278.

Carranza, E.J.M., Martin, H., 1997. A catchment basin approach to the analysis ofreconnaissance geochemical-geological data from Albay Province, Philippines.J. Geochem. Explor. 62, 157–171.

Cavazza, W., Gandolfi, G., 1992. Diagenetic processes along a basin-wide markerbed as a function of burial depth. J. Sediment. Petrol. 62, 261–272.

Chandrajith, R., Dissanayake, C.B., Tobschall, H.J., 2000. The stream sedimentgeochemistry of the Walawe Ganga basin of Sri Lanka—implications forGondwana mineralization. Gondwana Res. 2, 189–204.

Cipriani, C., Malesani, P.G., 1963a. Ricerche sulle arenarie: VII La composizionemineralogica di una serie di rocce della formazione Marnoso-arenacea.Periodico di Mineralogia 32, 302–342.

Cipriani, C., Malesani, P.G., 1963b. Ricerche sulle arenarie: VIII determinazioni


microscopiche sulle arenarie delle formazioni del Macigno eMarnoso-arenacea. Periodico di Mineralogia 32, 343–385.

Cipriani, C., Malesani, P.G. 1963c. Ricerche sulle arenarie: IX Caratterizzazione edistribuzione geografica delle arenarie appenniniche oligoceniche emioceniche. Memorie della Società Geologica Italiana 4, 339–375.













http://refhub.elsevier.com/S0009-2819(15)30019-2/sbref0005











































































































































































































































































































































































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H

J

J

J

K

L

L

L

L


V. Lancianese, E. Dinelli / Ch

ocker, M.D., 1999. Geochemical mapping in Georgia, USA: a tool forenvironmental studies, geologic mapping and mineral exploration. J. Geochem.Explor. 67, 345–360.

ondie, K.C., Philip, D.N.J., Conway, C.M., 1992. Geochemical and detrital modeevidence for two sources of early proterozoic. Sediment. Geol. 77, 51–76.

ondie, K.C., 1993. Chemical composition and evolution of upper continental crust:contrasting results from surface samples and shales. Chem. Geol. 104, 1–37.

onti, S., 2001. Gli intervalli pelitici della Formazione Marnoso-arenacea delMugello (Miocene medio): relazioni fra tettonica, fluidi freddi e instabilitàsedimentaria. Bollettino Società Geologica Italiana 120, 125-138.

ornamusini, G., Martelli, L., Conti, P., Pieruccini, P., Benini, A., Bonciani, F.,Callegari, I., Carmignani, L., 2002. Note illustrative della Carta Geologica d’Italiaalla scala 1:50.000, Foglio 266 Mercato Saraceno, ISPRA-Servizio Geologicod’Italia, Regione Emilia Romagna.

arnley, A.G., 1990. International geochemical mapping: a new global project. J.Geochem. Explor. 39, 1–13.

as, B.K., AL-Mikhlafi, A.S., Kaur, P., 2006. Geochemistry of Mansar Lake sediments,Jammu, India: Implication for source-area weathering, provenance andtectonic setting. J. Asian Earth Sci. 26, 649–668.

emetriades, A., 2014. Basic Considerations: Sampling, the Key for a SuccessfulApplied Geochemical Survey for Mineral Exploration and EnvironmentalPurposes. Reference Module in Earth Systems and Environmental Sciences,from Treatise on Geochemistry (Second Edition) 15, 1-31.

inelli, E., Lucchini, F., Mordenti, A., Paganelli, L., 1999. Geochemistry ofOligocene–Miocene sandstones of the northern Apennines (Italy) andevolution of chemical features in relation to provenance changes. Sediment.Geol. 127, 193–207.

inelli, E., Tateo F., Summa V., 2007. Geochemical and mineralogical proxies forgrain size in mudstones and siltstones from the Pleistocene and Holocene ofthe Po River alluvial plain, Italy. In José Arribas, Salvatore Critelli, and Mark J.Johnsson (Eds) Sedimentary Provenance and Petrogenesis: Perspectives fromPetrography and Geochemistry. Geological Society of America Special Paper,420, 25-36.

ypvik, H., Harris, N.B., 2001. Geochemical facies analysis of fine-grainedsiliciclastics using Th/U, Zr/Rb and (Zr + Rb)/Sr ratios. Chem. Geol. 181,131–146.

ontes, C., Mélièrès, F., Gibert, E., Liu, Q., Gasse, F., 1993. Stable isotope andradiocarbon balances of two Tibetan lakes (Sumxi Co, Longmu Co) from 13,000yr B.P. Quat. Sci. Rev. 12, 875–887.

örstner, U., Müller, G., 1974. Schwermetalle in Flussen und Seen als Ausdruck derUmweltverschmutzung. Springer, Berlin, pp. 225.

ralick, P.W., Kronberg, B.I., 1997. Geochemical discrimination of clasticsedimentary rock sources. Sediment. Geol. 113, 111–124.

ranzini, M., Leoni, L., Saitta, M., 1972. A simple method to evaluate the matrixeffects in X-ray fluorescence analysis. X-Ray Spectrom. 1, 151–154.

ranzini, M., Leoni, L., Saitta, M.,1975. Revisione di una metodologia analitica perfluorescenza-X basata sulla correzione completa degli effetti di matrice.Rendiconti della Società Italiana di Mineralogia e Petrologia 31, 365-378.

andolfi, G., Paganelli, L., Zuffa, G.G., 1983. Petrology and dispersal patterns in theMarnoso-arenacea formation (Miocene, Northern Apennines). J. Sediment.Petrol. 53, 493–507.

andolfi, G., Paganelli, L., Cavazza, W., 2007. Heavy-minerals associations astracers of limited compositional mixing during turbiditic sedimentation of theMarnoso-arenacea formation (Miocene, Northern Apennines, Italy). Dev.Sedimentol. 58, 621–645.

arcia, D., Ravenne, C., Maréchal, B., Moutte, J., 2004. Geochemical variabilityinduced by entrainment sorting: quantified signals for provenance analysis.Sediment. Geol. 171, 113–128.

ale, M., Plant, J.A., 1994. Drainage geochemistry. In: Govett, G.S.J. (Ed.), Handbookof Exploration Geochemistry, vol. 6. Elsevier Science, Amsterdam, p. 766.

iscott, R.N., 1984. Ophiolitic source rocks for Taconic-age flysch: trace-elementevidence. Geol. Soc. Am. Bull. 95, 1261–1267.

anousek, V., Farrow, C.M., Erban, V., 2006. Interpretation of whole-rockgeochemical data in igneous geochemistry: introducing Geochemical datatoolkit (GCDkit). J. Petrol. 47, 1255–1259.

in, Z.D., Wang, S., Shen, J., Zhang, E., Ji, J., Li, F., Lu, X., 2001. Chemical weatheringsince the little ice age recorded in lake sediments: a high-resolution proxy ofpast climate. Earth Surf. Process Landforms 26, 775–782.

in, Z.D., Wang, S., Shen, J., Wang, Y., 2003. Carbonate versus silicate Sr isotope inlake sediments and its response to the little ice age. Chin. Sci. Bull. 48, 95–100.

rishnamurthy, R.V., Bhattacharya, S.K., Kusumgar, S., 1986. Palaeoclimaticchanges deduced from 13C/12C and C/N ratios of Karewa lake sediments,India. Nature 323, 150–152.

aird, K.R., Cumming, B.F., Wunsam, S., Rusak, J.A., Oglesby, R.J., Fritz, S.C., Leavitt,P.R., 2003. Lake sediments record large-scale shifts in moisture regimes acrossthe northern prairies of north America during the past two millennia. Proc.Natl. Acad. Sci. 100, 2483–2488.

ancianese, V., Dinelli, E., 2014. Different spatial methods in regional geochemicalmapping at high density sampling: an application on stream sediments ofRomagna Apennines, Northern Italy. J. Geochem. Explor., http://dx.doi.org/10.1016/j.gexplo.2014.12.014, in press, accepted manuscript, available online 26




December 2014.ast, W.M., Smol, J.P. (Eds.), 2001. Tracking Environmental Change Using Lake

Sediments. Kluwer Academic Publishers, Dordrecht, The Netherlands.e Maitre, R.W., 1976. The chemical variability of some common igneous rocks. J.

Petrol. 17, 589–598.

PRESSer Erde xxx (2015) xxx–xxx 13

Leoni, L., Saitta, M., 1976. X-ray fluorescence analysis of 29 trace elements in rockand mineral standard. Rendiconti della Società Italiana di Mineralogia ePetrologia 32, 497-510.

Leoni, L., Menichini, M., Saitta, M., 1986. Determination of S, Cl, and F in silicaterocks by X-ray fluorescence analyses. X-Ray Spectrom. 11, 156–158.

Levene, H., 1960. Robust tests for the equality of variances. In: Olkin, I. (Ed.),Contributions to Probability and Statistics. Standford University Press, PaloAlto, CA, USA, pp. 278–292.

Levinson, A.A., 1974. Introduction to exploration geochemistry.Li, Y.H., 1991. Distribution patterns of the elements in the ocean: a synthesis.

Geochim. Cosmochim. Acta 55, 223–240.Lima, A., De Vivo, B., Cicchella, D., Cortini, M., Albanese, S., 2003. Multifractal IDW

interpolation and fractal filtering method in environmental studies: anapplication on regional stream sediments of (Italy), Campania region. Appl.Geochem. 18, 1853–1865.

Lucente, C.C., 2004. Topography and paleogeographic evolution of a middleMiocene foredeep basin plain (northern Apennines, Italy). Sediment. Geol. 170,107–134.

Martelli, L., Farabegoli, E., Benini, A., De Donatis, M., Severi, P., Pizziolo, M., Pignone,R., 1994. La geologia del Foglio 265–S. Piero in Bagno, in: La cartografiaGeologica della Emilia Romagna. Servizio Cartografico e Geologico, RegioneEmilia Romagna, Bologna.

McDonough, W.F., 1991. Partial melting of subducted oceanic crust and isolation ofits residual eclogitic lithology. Philos. Trans. R. Soc. 335, 407–418.

McLennan, S.M., Taylor, S.R., 1983. Geochemical evolution of the Archean shalesfrom South Africa: I. The Swaziland and Pongola supergroups. PrecambrianRes. 22, 93–124.

McLennan, S.M. 1989. Rare earth elements in sedimentary rocks: influence ofprovenance and sedimentary processes. In: Lipin, B.R., McKay, G.A. (eds.)Geochemistry and Mineralogy of Rare Earth Elements. Mineralogical Society ofAmerica, Reviews in Mineralogy 21, 169–200.

McLennan, S.M., Hemming, S., McDaniel, D.K., Hanson, G.N., 1993. Geochemicalapproach to sedimentation, provenance, and tectonics. Special Paper—Geol.Soc. Am. 284, 21–40.

Meyers, P.A., Eadie, B.J., 1993. Sources, degradation and recycling of organic matterassociated with sinking particles in Lake Michigan. Org. Geochem. 20, 47–56.

Meyers, P.A., Lallier-vergés, E., 1999. Lacustrine sedimentary organic matterrecords of late quaternary paleoclimates. J. Paleolimnol. 21, 345–372.

Morgan, J.W., Higuchi, H., Takahashi, H., Hertogen, J., 1978. Chondritic eucriteparent body—inference from trace-elements. Geochim. Cosmochim. Acta 42,27–38.

Mullins, H.T., 1998. Environmental change controls of lacustrine carbonate, Cayugalake, New York. Geology 26, 443–446.

Mutti, E., Ricci Lucchi, F., Roveri, M., 2002. Revisiting turbidites of theMarnoso-arenacea Formation and their basin-margin equivalents: problemswith classic models. In: Excursion Guidebook, Workshop organized byDipartimento di Scienze della Terra (Università di Parma) and Eni-DivisioneAgip, 64th EAGE Conference & Exhibition, Florence (Italy), May 27–30, p. 120.

Mutti, E., Tinterri, R., Benevelli, G., di Biase, D., Cavanna, G., 2003. Deltaic, mixed andturbidite sedimentation of ancient foreland basins. Mar. Pet. Geol. 20, 733–755.

Muzzi Magalhaes, P., Tinterri, R., 2010. Stratigraphy and depositional setting ofslurry and contained (reflected) beds in the Marnoso-arenacea formation(Langhian–Serravallian) northern Apennines, Italy. Sedimentology 57,1685–1720.

Nesbitt, H.W., Young, G.M., 1996. Petrogenesis of sediments in the absence ofchemical weathering: effects of abrasion and sorting on bulk composition andmineralogy. Sedimentology 42, 341–358.

Nesbitt, H.W., Young, G.M., McLennan, S.M., Keays, R.R., 1996. Effects of chemicalweathering and sorting on the petrogenesis of siliciclastic sediments, withimplications for provenance studies. J. Geol. 104, 525–542.

Ohta, A., Imai, N., Terashima, S., Tachibana, Y., 2005. Influence of surface geologyand mineral deposits on the spatial distributions of elemental concentrationsin the stream sediments of Hokkaido, Japan. J. Geochem. Explor. 86, 86–103.

Ohta, A., Imai, N., Terashima, S., Tachibana, Y., Ikehara, K., Nakajima, T., 2004.Geochemical mapping in Hokuriku, Japan: influence of surface geology,mineral occurrences and mass movement from terrestrial to marineenvironments. Appl. Geocheme. 19, 1453–1469.

Ortiz, E., Roser, B.P., 2006a. Geochemistry of stream sediments from the Hino RiverSW Japan: source rock signatures downstream compositional variations, andinfluence of sorting and weathering. Earth Sci. (Chikyu Kagaku) 60, 131–146.

Ortiz, E., Roser, B.P., 2006b. Major and trace element provenance signatures inmodern stream sediments from the Kando river, San’in district, SW Japan. Isl.Arc. 15, 223–238.

Puchelt, H., 1992. Environmental inorganic geochemistry of the Continental crust.In: Hutzinger, O. (Ed.), The Handbook of the Environmental Chemistry.Springer-Verlag, Berlin, pp. 27–63.

Ranasinghe, P.N., Fernando, G.W.A.R., Dissanayake, C.B., Rupasinghe, M.S., 2008.Stream sediment geochemistry of the upper Mahaweli river basin of SriLanka—geological and environmental significance. J. Geochem. Explor. 99,1–28.

Ranasinghe, P.N., Fernando, G.W.A.R., Dissanayake, C.B., Rupasinghe, M.S., Witter,


D.L., 2009. Statistical evaluation of stream sediment geochemistry ininterpreting the river catchment of high-grade metamorphic terrains. J.Geochem. Explor. 103, 97–114.

Reimann, C., de Caritat, P., 1998. Chemical Elements in the Environment.Factsheets for the Geochemist and Environmental Scientist. Springer, pp. 398.




































































































































































































































































































































































































































dx.doi.org/10.1016/j.gexplo.2014.12.014

















































































































































































































































































































































































































































































































































































































ING ModelC

1 emie d

R

R

R

R

R

R

R

R

R

R

R

R

Zattin, M., Zuffa, G.G., 2004. Unravelling the Source Rocks of Late Eocene-MioceneOrogenic Wedge and Foredeep Arenites of the Northern Apennines and


4 V. Lancianese, E. Dinelli / Ch

eimann, C., Matschullat, J., Birke, M., Salminen, R., 2010. Antimony in theenvironment: lessons from geochemical mapping. Appl. Geochem. 25,175–198.

icci Lucchi, F., 1978. Turbidite dispersal in a Miocene deep-sea plain. Geol.Mijnbouw 57, 559–576.

icci Lucchi, F., 1981. The Marnoso arenacea turbidites, Romagna and UmbriaApennines. Excursion guidebook, with contribution on sedimentology of someitalian basins In: F. Ricci Lucchi (Ed.), 2nd IAS Eur. Meeting, Bologna, 229–303.

icci Lucchi, F., 1986. The Oligocene to recent foreland basins of the NorthernApennines. In: Allen, P.A., Homewood, P. (Eds.), Foreland Basins. BlackwellScientific, Oxford, pp. 105–139, IAS Spec. Publ. 8.

icci Lucchi, F., Ori, G.G., 1985. Field Excursion D: syn-orogenic deposits of amigrating basin system in the NW Adriatic Foreland: examples from EmiliaRomagna region, Northern Apennines. International Symposium on ForelandBasins In: Allen, P.A., Homewood, P., Williams, G., (Eds.), Excursion Guidebook,137-176.

icci Lucchi, F., Pialli, G., 1973. Apporti Secondari Nella Marnoso-ArenaceaTorbiditi di Conoide e di Pianura Sottomarina a Est-Nordest di Perugia, vol. 92.Bollettino della Società Geologica, Italiana, pp. 669–712.

icci Lucchi, F., Valmori, E., 1980. Valmori Processi e meccanismi disedimentazione. Sedimentologia 2, 212, CLUEB Bologna.

ose, A.W., Hawkes, H.E., Webb, J.S., 1979. Geochemistry in Mineral Exploration.Academic Press, London.

ose, N.L., Boyle, J.F., Du, Y., Yi, C., Dai, X., Appleby, P.G., Bennion, H., Cai, S., Yu, L.,2004. Sedimentary evidence for changes in the pollution status of Taihu in theJiangsu region of eastern China. J. Paleolimnol. 32, 41–51.

oser, B.P., Korsch, R.J., 1986. Determination of tectonic setting ofsandstone–mudstone suites using SiO2 content and K2O/Na2O ratio. J. Geol.94, 635–650.

oser, B.P., Korsch, R.J., 1988. Provenance signatures of sandstone–mudstonesuites determined using discriminant function analysis of major-element data.Chem. Geol. 67, 119–139.




overi, M., Ricci Lucchi, F., Lucente, C.C., Manzi, V., Mutti, E., 2002. Stratigraphy,facies and basin fill history of the Marnoso- arenacea Formation. Revisitingturbidites of the Marnoso-arenacea Formation and their basin-marginequivalents: problems with classic models In: E., Mutti, F., Ricci Lucchi, M.,Roveri, (Eds.). Excursion Guidebook, Università di Parma and Eni-Agip


Division, 64th EAGE Conference and Exhibition, Florence (Italy), pp.120.Servizio Geologico, Sismico e dei Suoli Regione Emilia Romagna. <http://geo.

regione.emilia-romagna.it/geocatalogo/> (last accessed 13.11.14.).Singh, P., 2010. Geochemistry and provenance of stream sediments of the Ganga

River and its major tributaries in the Himalayan region, India. Chem. Geol. 269,220–236.

Swennen, R., Van der Sluys, J., 1998. Zn, Pb, Cu and As distribution patterns inoverbank and medium-order stream sediment samples: their use inexploration and environmental geochemistry. J. Geochem. Explor. 65, 27–45.

Talling, P.J., Amy, L.A., Wynn, R.B., Blackbourn, G., Gibson, O., 2007. Evolution ofturbidity currents deduced from extensive thin turbidites: Marnoso arenaceaformation (Miocene), Italian Apennines. J. Sediment. Res. 77, 172–196.

Taylor, S.R., McLennan, S.M., 1985. The Continental Crust: Its Composition andEvolution. Blackwell, Oxford, pp. 312.

Tinterri, R., Muzzi Magalhaes, P., 2011. Synsedimentary structural control onforedeep turbidites: an example from Miocene Marnoso-arenacea formation,Northern Apennines, Italy. Mar. Pet. Geol. 28, 629–657.

Tripathy, G.R., Singh, S.K., Ramaswamy, V., 2013. Major and trace elementgeochemistry of Bay of Bengal sediments: implications to provenances andtheir controlling factors. Palaegeogr. Palaeoclimatol. Palaecol., in press,available online 22 April 2013, ISSN 0031-0182, http://dx.doi.org/10.1016/j.palaeo.2013.04.012.

Turekian, K.K., Wedephol, K.H., 1961. Distribution of elements in some major unitsof the Earth’s crust. Geol.Soc, Am, Bull 72, 175–192.

Vital, H., Stattegger, K., 2000. Major and trace elements of stream sediments fromthe lowermost Amazon River. Chem. Geol. 168, 151–168.

Wedepohl, K.H., 1995. The composition of the continental crust. Geochimi.Cosmochim. Acta 59, 217–239.

Willemse, N.W., Tornqvist, T.E., 1999. Holocene century-scale temperaturevariability from West Greenland lake records. Geology 27, 580–584.


Southern Alps, vol. 123. Bollettino della Società Geologica, Italiana, pp. 67–76.Zuffa, G.G., 1980. Hybrid arenites: their composition and classification. J. Sediment.

Petrol. 50, 21–29.







































































































































































http://geo.regione.emilia-romagna.it/geocatalogo/




















































































































http://dx.doi.org/10.1016/j.palaeo.2013.04.012





















































































































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