Sub Action 2 1 - ZeoLIFE project

Transcription

LIFE+2010 – Project code: LIFE+10ENV/IT/000321 – Action 2 – UniMORE - Technical Report
WATER POLLUTION REDUCTION AND WATER SAVING
USING A NATURAL ZEOLITITE CYCLE
LIFE+2010 – Project code: LIFE+10ENV/IT/000321
Technical report on:
Mineralogical features of the quarry materials
Deliverable product of the UniMORE Research Units
Code of the associated action: 2
Deadline: February 29, 2012
Angela Laurora
Maria Giovanna Vezzalini
Maria Franca Brigatti
Daniele Malferrari
1
Disclaimer
This report has been produced with the financial assistance of the European Union - LIFE+
Environment - GA LIFE+10ENV/IT/000321. The contents of this report are the sole responsibility
of the ZeoLIFE Consortium and can under no circumstances be regarded as reflecting the position
of the European Union.
Summary
The first purpose of Action 2 is to find a zeolitite quarry characterized by a high and sufficiently
constant zeolite content, adequate values of Cation Exchange Capacity (CEC), and presence of
zeolite species effective in NH4 adsorption and subsequent release in controlled conditions; amount
of available raw material and quarry location are considered, as well.
The K-rich, Na-poor zeolitite from the Piandirena quarry (Sorano, Gr) resulted to be a first-rate
material for the project purposes. It is, in fact, characterized by high zeolitic content (with
dominant chabazite and very subordinate phillipsite), as well as by high CEC value. When
compared to other ones in central Italy, this quarry presents further valuable aspects such as: i) the
shortest distances to the location of the experimental field; ii) large reserve of raw material; iii)
availability of raw material, whose technologic properties are perfectly suitable for the purposes of
the present project, available in dumps; iv) presence of a crushing and sieving apparatus, thus
rendering available, directly in the quarry, a semi-finished ground product.
2
Technical report on mineralogical
features of the quarry materials
Aims and description of the activities
One of the aim of the activities proposed in Action 2, for which the UniMORE unit is responsible, is the
selection of a suitable zeolitite quarry material. The criteria adopted for the selection include: easy access
to the quarries, low total costs (also including the transport to the experimental field, located in Codigoro,
Ferrara province), high and possibly constant zeolite content, adequate values of Cation Exchange Capacity
(CEC), and presence of zeolite species effective in NH4 adsorption and subsequent release in controlled
conditions.
As previously stated in Part B and Part C of the Technical Application Form of the present project,
chabazite-bearing zeolitite deposits are widespread in Central Italy (Tuscany, Latium), with several quarries
already exploiting them. As demonstrated by plenty of experimental scientific works (Passaglia & Azzolini,
1994; Passaglia & Poppi, 2005; Passaglia et al., 1997; Passaglia et al., 1998a,b), chabazite is very effective
not only in NH4 uptake from swine manure, but also in successive controlled NH4 release in soils. This latter
aspect of chabazite behavior plays a key role in the present project, which is focused on NH4 abatement in
swine manure, as well as on NH4-charged chabazite recycling as soil amendment capable of reducing the
amount of synthetic fertilizers and irrigation water in open field cultivation. Other zeolite species, such as
phillipsite, have great potential for NH4 adsorption and retention, but not the same ability as chabazite in
exchanging NH4 with circulating solutions and plant root systems in soils.
The main goal of the UniMORE unit in Action 2 during the first six months of project development was thus
to carry out a chemical and physical, as well as mineralogical characterization of several zeolitite samples
coming from different quarries located in Central Italy, in order to select the most suitable raw material to
be used throughout the entire project. Besides the technological properties of the material, the final choice
also took into account factors of environmental and economic concern.
For the evaluation of the most suitable raw material, samples from the following seven localities were
analyzed: Sorano (Gr), Sovana (Gr), Farnese (Vt), Grotte Santo Stefano (Vt), Corchiano (Vt), Nepi (Vt), and
Riano (Rm) (Fig. 1). As more detailed hereafter, all the mentioned localities are in Central Italy, and the
examined chabazite-bearing zeolitite deposits are the closest to the experimental field. Everywhere
quarrying is carried out in vertical stopes; non marketable material, namely broken blocks or blocks with
irregular shape and size, is discharged on adjacent slopes or in already exploited stopes, where it forms big
dumps. This material is an already available reserve of zeolitic tuff for the purposes of the present project.
Other zeolitite deposits, located further south in the Italian Peninsula, in the islands (Sardinia) or abroad
(Greece, Slovakia, Serbia, Hungary), were not taken into account because of lack of quarries, predominance
of zeolite species less effective than chabazite in NH4 adsorption and release, high Na content (see
paragraph “Discussion of analytical results”), or expensive transport of the quarried material.
3
Fig. 1 – Geographical sketch showing the location of the seven investigated zeolitite quarries in Central Italy. The location of the
experimental field (Codigoro), and of some of the most important cities in the zone of interest is also reported for the sake of
clarity.
4
For each examined sample, quantitative mineralogical analysis (with determination of zeolite total
content), whole rock chemical composition analysis, determination of Cation Exchange Capacity (CEC),
apparent density, and water retention were performed. Once the most suitable quarry material was
selected on the basis of the above-mentioned criteria, a further chemical analysis of the main zeolite
species was carried out.
Analytical techniques
In order to obtain representative samples from each examined locality, an appropriate procedure was followed by
picking out a total amount of 10 kg of raw material from different points of the quarries. The collected material was
accurately ground, and repeatedly quartered until obtaining the needed sample amount.
Quantitative mineralogical analyses were carried out via a X'Pert PRO - PANAlytical diffractometer. Diffractometric
measurements interpretation was performed using the Rietveld method via the General Structure Analysis System
(GSAS) software package by Larson & Von Dreele (2004), combined with the Reference Intensity Ratio (RIR) method
for the determination of the amorphous phase (Gualtieri, 1996; Gualtieri, 2000).
Whole rock chemical analysis was carried out on pressed pellets via a wavelength-dispersive Philips PW 1480 X-Ray
Fluorescence (XRF) spectrometer, using the methods of Franzini et al. (1975) and Leoni & Saitta (1976) for the
determination of element concentrations. Fe was assumed to be in its trivalent oxide form. Loss On Ignition (LOI) was
determined by sample heating in a oven at 1100°C. The analysis was normalized to 100 wt% for major element oxides,
and is considered accurate to within 2-5% for major elements and better than 10% for minor and trace elements.
2+
2+
+
+
CEC determination of exchanged Ca , Mg , Na , and K cations was performed via elution of suitably powdered
samples in a Gooch filter with porosity 2 by a 1N NH 4 solution, obtained by dissolving “suprapure” NH4Cl in millipore
water. The elution was carried out until the concentration of each single cation in the last 1L flask was less than 0.5
2+
2+
+
+
mg/L. Measurements of Ca , Mg , Na , and K concentrations were carried out on each 1L flask of eluted solution by
a Perkin-Elmer 303 Atomic Absorption Spectrometer (AAS). The final CEC value was given by the sum of the total
2+
2+
+
+
measured concentrations of Ca , Mg , Na , and K in the overall eluted solution, each total cation concentration
being divided by the corresponding equivalent cation weight. Estimated detection limit for the analytical technique is
0.01 meq/g.
Apparent density was determined as the ratio between the mass of ground sample which fills a measuring cup in
loose conditions and the volume of the cup (250 cc). The ground sample was previously sieved in order to obtain two
different grain sizes, i.e. <3 mm and 3-6 mm, corresponding to those of the two semi-finished products available at
the Piandirena quarry (see Conclusions). The measurement of apparent density was performed on both grain sizes.
Water retention was determined by putting 250 g of ground sample in a column with the drain hose clamped, and
pouring in it 250 cc of deionized water to cover the sample. After one hour, the drain hose was unclamped, and the
drained water was collected in a measuring cup. The water retention was then calculated by subtracting the volume of
drained water from the amount of water used originally. The ground sample was previously sieved in order to obtain
two different grain sizes, i.e. <3 mm and 3-6 mm, corresponding to those of the two semi-finished products available
at the Piandirena quarry (see Conclusions). The measurement of water retention was performed on both grain sizes.
Chemical analysis was performed on zeolite crystalline aggregates via an ARL-SEMQ electron microprobe in
wavelength-dispersive mode, using the software package by Donovan (1995). Natural minerals were used as
standards. Results are considered accurate within 2-6%. Calculated chemical formulae were based on 24 oxygen
atoms. Water content was measured via a Seiko SSC 5200 thermal analyzer on ∼25 mg of ground picked up zeolite
grains.
5
Geological setting of the selected localities and description of the obtained analytical results
Sorano (Gr)
The town of Sorano (Grosseto Province, Tuscany) is about 80 km SE of the provincial capital and 20 km NW
of the Bolsena lake. It is about 380 km away from the town of Codigoro (Ferrara Province), where the
experimental field is located.
The analyzed sample comes from a quarry named by the inhabitants as Piandirena, located on the N side of
the road S.P. n.4, between km 12.5 and km 12.9. As a whole, the quarry extends over an area of about
60.000 m2. At present this is the most important active quarry in the zone. The exploited material comes
from a tough, highly zeolitized body known as Lithic Yellow Tuff (Sorano Formation, distributed over the N,
S, and W sectors of the Làtera Volcanic Complex; Vezzoli et al., 1987). This unit consists of two similar types
of deposits. The lower is an ash deposit, with an overall light yellowish grey color, containing white or light
grey, very vesicular pumice. The average size of pumice fragments ranges between 1 and 2 cm. The upper
deposit is constituted by an ashy or micropumiceous matrix of light, yellowish grey color, containing pumice
fragments up to centimetric size. Although the whole unit is very consolidated and tough, thin layers of
poorly consolidated or even loose material may occur at the base of the lower deposit. The Lithic Yellow
Tuff overlies the Red Tuff with Black Pumice unit, the contact between the two units being clearly visible on
the quarry walls.
Analytical results
Quantitative mineralogical analysis (wt% with standard deviations in brackets):
chabazite 68.5 (0.9); phillipsite 1.8 (0.4); analcime 0.6 (0.3)*; mica 5.3 (0.6); K-feldspar 9.7 (0.7); pyroxene
2.9 (0.4); volcanic glass 11.2 (1.0).
*Complete analcimization of leucite was assumed in the Rietveld refinement (Gupta & Fyfe, 1975).
Total zeolitic content (wt%) (Fig.2):
70.9, of which 68.5 is chabazite, 1.8 phillipsite, and 0.6 analcime.
Whole rock chemical composition:
Major elements
(wt% oxides)
Minor and trace
elements (ppm)
SiO2
52.61
Ni
<8
Al2O3
17.12
Co
11
Fe2O3
3.32**
Cr
8
TiO2
0.49
V
42
P2O5
0.14
Pb
32
MnO
0.10
Zn
31
MgO
1.56
As
<8
CaO
5.32
Cu
<20
6
Na2O
0.68
Cd
<2
K2O
6.14
S
110
H2O
15.52
Cl
50
Total
100.00
**Iron content possibly due to the presence of low amounts of iron compounds (oxides/hydroxides or sulphides),
eventually characterized by poor crystallinity and non identifiable by the Rietveld-RIR method.
Cation Exchange Capacity (CEC in meq/g with standard deviation in brackets) (Fig. 3):
2.17 (0.10) of which 1.46 is due to Ca, 0.04 to Mg, 0.07 to Na, and 0.60 to K.
Apparent density (g/cm3):
0.87 (<3 mm); 0.56 (3-6 mm).
Water retention (wt%):
48.4 (<3 mm); 34.2 (3-6 mm).
Sovana (Gr)
The town of Sovana (Grosseto Province, Tuscany) is less than 10 km SW of the town of Sorano. It is about
390 km away from the town of Codigoro (Ferrara Province), where the experimental field is located.
The analyzed sample comes from a quarry named by the inhabitants as Campimaglia, located on the SE side
of the road S.P. n.22 linking Sorano (Gr) to Sovana (Gr). The exploited material is dug out of the upper flow
unit of the so-called Sovana Formation (the most widely distributed within the Làtera Volcanic Complex;
Vezzoli et al., 1987). This upper flow unit is a massive, fairly coherent, highly zeolitized body, 4 to 15 m
thick. It consists of a tawny red groundmass made of glassy fragments and crystals of sanidine, leucite and
clinopyroxene containing centimetric to decimetric black pumice with analcimized leucite and sanidine. It is
currently described as Micropumiceous Red Ignimbrite with Black Pumice. When present, the lower flow
unit of the Sovana Formation is a poorly coherent or unconsolidated deposit of light grey pumice.
Analytical results
chabazite 44.1 (0.7); phillipsite 13.8 (0.7); analcime 1.4 (0.3)*; mica 5.6 (0.5); K-feldspar 14.5 (0.8);
plagioclase 6.6 (0.8); pyroxene 1.9 (0.5); volcanic glass 12.1 (1.0).
7
Major elements
(wt% oxides)
Minor and trace
elements (ppm)
SiO2
51.88
Ni
7
Al2O3
16.40
Co
5
Fe2O3
3.80**
Cr
8
TiO2
0.55
V
75
P2O5
0.16
Pb
81
MnO
0.13
Zn
63
MgO
1.70
As
22
CaO
5.58
Cu
< 10
Na2O
0.84
Cd
<7
K2O
7.36
S
142
H2O
11.60
Cl
48
Total
100.00
0.90 (<3 mm); 0.59 (3-6 mm).
48.6 (<3 mm); 33.8 (3-6 mm).
Farnese (Vt)
The town of Farnese (Viterbo Province, Latium) is about 43 km NW of the provincial capital. It is about 390
km away from the town of Codigoro (Ferrara Province), where the experimental field is located.
The analyzed sample comes from a quarry located on the E side of the road S.P. n.106 linking Casa Fattorale
(municipality of Canino, Vt) to Case Monterozzi (municipality of Canino, Vt), exploiting the massive levels of
the so-called Farnese Formation (Vezzoli et al., 1987), a single, up to 5 m thick, pumice flow deposit, which
can vary from unconsolidated to coherent, with white and gray pumice in white ashy matrix. The Farnese
Formation is overlapped by the above-mentioned Sovana Formation.
Analytical results
8
Major elements
(wt% oxides)
Minor and trace
elements (ppm)
SiO2
51.30
Ni
7
Al2O3
18.20
Co
4
Fe2O3
5.60**
Cr
5
TiO2
0.52
V
63
P2O5
0.16
Pb
88
MnO
0.10
Zn
41
MgO
1.83
As
25
CaO
3.95
Cu
<7
Na2O
1.52
Cd
<5
K2O
6.12
S
130
H2O
10.70
Cl
40
Total
100.00
0.96 (<3 mm); 0.65 (3-6 mm).
48.7 (<3 mm); 33.5 (3-6 mm).
9
Grotte Santo Stefano (Vt)
Grotte Santo Stefano, a village in the municipality of Viterbo (Viterbo Province, Latium), is about 18 km NE
of the provincial capital and about 23 km E of the Bolsena lake. It is about 400 km away from the town of
Codigoro (Ferrara Province), where the experimental field is located.
The analyzed sample comes from a quarry located 0.5 km S of the village of Vallebona (municipality of
Viterbo), exploiting a tough pyroclastic unit constituted by leucititic tuffs with phenoclasts of pyroxene,
abundant pumice, and little fragments of different types of rock. It shows alternating levels with colors
variable from grey to yellowish; pedogenized levels are also present (see notes to the geological sheet n.
137 “Viterbo” of the Geological Map of Italy at the scale 1:100.000 edited in 1970 by the Geologic Service
of Italy).
Analytical results
Major elements
(wt% oxides)
Minor and trace
elements (ppm)
SiO2
50.22
Ni
3
Al2O3
18.30
Co
6
Fe2O3
6.10**
Cr
5
TiO2
0.60
V
72
P2O5
0.15
Pb
102
MnO
0.11
Zn
40
MgO
1.83
As
25
CaO
3.66
Cu
<9
Na2O
2.13
Cd
<7
K2O
6.50
S
120
H2O
10.40
Cl
40
Total
100.00
10
0.98 (<3 mm); 0.68 (3-6 mm).
48.5 (<3 mm); 33.6 (3-6 mm).
Corchiano (Vt)
The town of Corchiano (Viterbo Province, Latium) is about 30 km ESE of the provincial capital and about 20
km E of the Vico lake. It is about 420 km away from the town of Codigoro (Ferrara Province), where the
The analyzed sample comes from a quarry located on the W side of the road S.P. n.29 linking Corchiano (Vt)
to Civita Castellana (Vt), exploiting the most coherent, zeolitized levels of a tephritic-phonolithic ignimbritic
unit, with transitions to trachitic and latitic terms. The unit is characterized by the presence of pumice
varying in color from yellowish and reddish to black, with large phenocrystals of leucite and sanidine. The
compaction degree of the rocks depends on the intensity of the alteration processes (diagenesis)
undergone by the volcanic products. The freshest parts are unconsolidated and dark grey in color (the socalled “pozzolana”), whereas the most altered parts are reddish-yellow in color with few black pumice.
These “hardened” levels of the ignimbritic unit are usually referred to as Lithoid Tuff with Black Pumice (see
notes to the geological sheet n. 137 “Viterbo” of the Geological Map of Italy at the scale 1:100.000 edited in
1970 by the Geologic Service of Italy).
Analytical results
Major elements
(wt% oxides)
Minor and trace
elements (ppm)
SiO2
49.80
Ni
5
Al2O3
19.35
Co
5
11
Fe2O3
5.35**
Cr
6
TiO2
0.55
V
65
P2O5
0.14
Pb
85
MnO
0.12
Zn
45
MgO
1.91
As
20
CaO
3.82
Cu
< 10
Na2O
1.64
Cd
<5
K2O
6.22
S
125
H2O
11.10
Cl
42
Total
100.00
0.95 (<3 mm); 0.64 (3-6 mm).
48.7 (<3 mm); 33.8 (3-6 mm).
Nepi (Vt)
The town of Nepi (Viterbo Province, Latium) is about 40 km SE of the provincial capital and about 20 km SE
of the Vico lake. It is about 430 km away from the town of Codigoro (Ferrara Province), where the
The analyzed sample comes from a quarry located N of Nepi, just outside the town, on the W side of the
Nepesina road (S.S. n.311). The exploited material is dug out of the zeolitized levels of the same tephriticphonolithic ignimbritic unit described for the Corchiano area (see notes to the geological sheet n. 143
“Bracciano” of the Geological Map of Italy at the scale 1:100.000 edited in 1971 by the Geologic Service of
Italy).
Analytical results
chabazite 52.3 (0.8); phillipsite 8.4 (0.6); analcime 1.2 (0.4); mica 2.7 (0.4); K-feldspar 4.4 (0.3); plagioclase
10.2 (0.5); pyroxene 2.5 (0.4); volcanic glass 18.3 (1.9).
12
Major elements
(wt% oxides)
Minor and trace
elements (ppm)
SiO2
50.18
Ni
8
Al2O3
17.95
Co
9
Fe2O3
4.68**
Cr
10
TiO2
0.59
V
102
P2O5
0.11
Pb
92
MnO
0.14
Zn
66
MgO
1.47
As
55
CaO
4.82
Cu
18
Na2O
0.89
Cd
5
K2O
6.37
S
135
H2O
12.80
Cl
48
Total
100.00
0.92 (<3 mm); 0.61 (3-6 mm).
48.4 (<3 mm); 33.5 (3-6 mm).
Riano (Rm)
The town of Riano (Rome Province, Latium) is about 40 km N of the capital and 30 km E of the Bracciano
lake. It is about 450 km away from the town of Codigoro (Ferrara Province), where the experimental field is
located.
The stratigraphy of the volcanic sequence at Riano is quite complex. Three different volcanic formations
can be recognized. From top to bottom, the first one (referred to as ß T in the geological sheet n. 144
13
“Palombara Sabina” of the Geological Map of Italy at the scale 1:100.000 edited in 1970 by the Geologic
Service of Italy) is characterized by alternating levels of ochre tuffs, yellow lithoid tuffs, lapilli, cinerite, cmsized leucitic scoriae, and white pumice; palosoils levels are seldom present. The second one (referred to as
τ- W in the geological sheet n. 144 of the Geological Map of Italy at the scale 1:100.000) is a trachitic to
trachiphonolitic massive ignimbrite named Red Tuff with Black Scoriae, constituted by a micropumiceous,
gray to blackish matrix containing black pumice fragments up to decimetric size; these pumice fragments
are vesiculated and often show preferential orientation. The third one (referred to as θ1T in the geological
sheet n. 144 of the Geological Map of Italy at the scale 1:100.000) is a caotic agglomerate with
micropumiceous yellow, reddish, and grey matrix with lapilli and crystals of leucite, clinopyroxene, and
mica; it also contains blocks of lava and clayey or calcareous metamorphosed xenoliths. Tuffs, varying from
unconsolidated to fairly coherent, and occasionally containing lapilli and ash, are intercalated with levels of
scoriae and lava fragments. Diatomite and alluvional lenses, as well as paleosoils, can be sometimes
recognized.
The analyzed sample comes from a quarry located SE of Riano, just outside the town, on the NE side of the
A1 highway (Diramazione Roma Nord). The exploited material is dug out of the second volcanic formation
described above, i.e. the zeolitized Red Tuff with Black Scoriae.
Analytical results
plagioclase 5.3 (0.5); pyroxene 1.1 (0.2); calcite 12.4 (0.2); volcanic glass 28.0 (1.0).
Major elements
(wt% oxides)
Minor and trace
elements (ppm)
SiO2
45.74
Ni
10
Al2O3
14.91
Co
8
Fe2O3
4.10**
Cr
10
TiO2
0.53
V
102
P2O5
0.16
Pb
78
MnO
0.12
Zn
44
MgO
1.97
As
35
CaO
9.77
Cu
<5
Na2O
0.76
Cd
<5
K2O
7.04
S
110
14
H2O
9.74
CO2
5.16
Total
Cl
33
100.00
0.91 (<3 mm); 0.60 (3-6 mm).
48.5 (<3 mm); 33.3 (3-6 mm).
Discussion of analytical results
From the performed quantitative mineralogical analyses and the histogram plotted in Fig. 2, it results that
the sample from Sorano (Gr) has the highest value of total zeolitic content (>70 wt%), followed by the
sample from Nepi (Vt), whose value, however, is almost 10 wt% lower. It is worthy of note that the sample
from Sorano (Gr) also has the highest chabazite content (68.5 wt%), which accounts for almost its total
zeolitic content; in this sample, chabasite represents the 97% of the zeolitic species. In the sample from
Nepi (Vt), chabazite represents the 85% of the zeolitic species, due to a significant contribution of phillipsite
(> 8 wt%) to the total zeolitic content.
When Cation Exchange Capacity (CEC) is taken into account, it results that Ca values are the highest in the
sample from Sorano (Gr) (1.46 meq/g), whereas K values are the highest in the sample from Nepi (Vt) (0.87
meq/g). K values are comparable in all the other samples (varying between 0.62 meq/g for Farnese (Vt) and
0.53 meq/g for Grotte Santo Stefano sample), with the exception of the sample from Riano, whose value is
remarkably lower (0.3 meq/g). Na values range from 0.13 to 0.15 meq/g in the samples from Farnese (Vt),
Grotte Santo Stefano (Vt), and Corchiano (Vt), are slightly lower in the samples from Sovana (Gr), Nepi (Vt),
and Riano (Rm) (varying between 0.12 meq/g for Sovana (Gr) and 0.10 meq/g for Nepi (Vt) and Riano (Rm)),
and are the lowest in the sample from Sorano (Gr) (0.07 meq/g). Despite the fact that its K and Na CEC
values are not the highest, the sample from Sorano (Gr) presents the most remarkable total CEC value,
mainly due to its high zeolitic content. It is worthy of note that samples with the highest Ca, Mg, Na, and K
CEC values have corresponding high whole rock Ca, Mg, Na, and K oxides contents, respectively. This is
because both CEC values and whole rock contents are strongly controlled by the high percentage of zeolite
(mainly chabasite and phillipsite) present in the samples.
The identification and quantification of the exchangeable cations are of paramount importance when
assessing both environmental impact and possible harvest improvement deriving from the introduction of
natural zeolitite as soil amendment. It is well known, for instance, that K is one of the primary plant
macronutrient, which is usually lacking from the soil first because plants use large amounts of it for their
15
growth and survival, whereas excessive Na contents can result in a nutrient imbalance and poor plant
growth. Noticeably, all the analyzed samples, and especially the sample from Sorano (Gr), have low
exchangeable Na+ contents, thus being very suitable for the purposes of the present project.
100
analcime
90
phillipsite
Total zeolitic content (wt%)
80
chabazite
70
60
50
40
30
20
10
0
Sorano
(Gr)
Sovana
(Gr)
Farnese
(Vt)
Grotte
Santo Stefano
(Vt)
Corchiano
(Vt)
Nepi
(Vt)
Riano
(Rm)
Fig. 2 – Stacked histogram of the total zeolite content in the analyzed samples from the seven selected zeolitite quarries in Central
Italy. The contribution of the three identified species chabazite, phillipsite, and analcime is shown.
2.5
K
Cation Exchange Capacity (CEC, meq/g)
Na
2
Mg
Ca
1.5
1
0.5
0
Sorano
(Gr)
Sovana
(Gr)
Farnese
(Vt)
Grotte
Santo Stefano
(Vt)
Corchiano
(Vt)
Nepi
(Vt)
Riano
(Rm)
Fig. 3 – Stacked histogram of the CEC values of the analyzed samples from the seven selected zeolitite quarries in Central Italy. The
contribution of Ca, Mg, Na, and K is shown.
16
For the localities of Sorano, Sovana, and Riano, we have found some references reporting, among other
data, the quantitative mineralogical composition for zeolitite samples coming from the same areas.
Unfortunately it is not possible to know the exact spatial relationships between samples considered for this
research and samples whose analyses are reported in literature. Data are summarized in the table
hereafter reported. Even if all the deviations detected through this study fall within the limits of variability
to which a quarry sample can be subject, literature data for sample from Sovana and Riano show quite
different deviances; on the other hand there is a very good agreement between our data and other data
from Sorano.
Comparison between the experimental results in this report and some data from literature on quantitative mineralogical
analyses for zeolitite samples from Riano, Sorano, and Sovana.
1
2
Chabazite Philipsite Analcime
K-feldspar ( )
Plagioclase ( )
Carnevali et al., 1994 (Riano)
49.8(2)
11.5(3)
5.3(2)
17.6(4)
3.1(3)
5
9.2(3)
26.3(2)
6.3(2)
23.4(3)
9.9(3)
6
Gualtieri & Brignoli, 2004 (Riano) ( )
8.7(3)
26.5(2)
6.6(3)
23.3(3)
9.7(3)
This report (Riano)
24.8(0.4)
4.7(0.4)
3.2(0.3)
15.4(0.4)
5.3(0.5)
Gualtieri et al., 1999 (Sorano-A)
70.4(9)
2.4(2)
1.1(2)
10.4(2)
n.d.
Gualtieri et al., 1999 (Sorano-B)
67.5(2)
9.1(4)
0.8(2)
14.9(2)
1.4(3)
De Gennaro et al., 2004 (Sorano)
61
n.d.
7
25
n.d.
Passaglia et al., 2005 (Sorano)
66.8(2.0)
2.1(0.5)
1.2(0.2)
9.5(1.0)
n.d.
This report (Sorano)
68.5(0.9)
1.8(0.4)
0.6(0.3)
9.7(0.7)
n.d.
Gualtieri et al., 1999 (Sovana)
27.2(7)
28.3(7)
n.d.
27.9(8)
3.9(3)
This report (Sovana)
44.1(0.7)
13.8(0.7)
1.4(0.3)
14.5(0.8)
6.6(0.8)
Calcite
Mica ( )
Pyroxene ( )
Smectite
Volc. glass
Carnevali et al., 1994 (Riano)
3
4
9.7(2)
n.d.
n.d.
n.d.
3.0 (average)
5
n.d.
3.9(3)
n.d.
n.d.
21(2)
6
n.d.
3.2(4)
n.d.
n.d.
22(2)
This report (Riano)
12.4(0.2)
5.1(0.6)
1.1(0.2)
n.d.
28.0(1.0)
Gualtieri et al., 1999 (Sorano-A)
1.5(1)
7.7(3)
1.6(3)
n.d.
4.9(9)
Gualtieri et al., 1999 (Sorano-B)
0.8(1)
4.1(3)
1.3(2)
n.d.
0.4(1)
De Gennaro et al., 2004 (Sorano)
n.d.
1
3
3
n.d.
Passaglia et al., 2005 (Sorano)
n.d.
6.6(1.2)
1.4(0.4)
n.d.
12.4(5.0)
This report (Sorano)
n.d.
5.3(0.6)
2.9(0.4)
n.d.
11.2(1.0)
Gualtieri et al., 1999 (Sovana)
2.3(2)
3.7(3)
2.1(2)
n.d.
4.6(8)
This report (Sovana)
n.d.
5.6(0.5)
1.9(0.5)
n.d.
12.1(1.0)
1
Notes: n.d., not detected; ( ) reported as sanidine in Carnevali et al. (1994), Gualtieri et al. (1999), Gualtieri & Brignoli
2
3
(2004), and Passaglia et al. (2005); ( ) reported as albite in Carnevali et al. (1994); ( ) reported as biotite in Carnevali et
4
al. (1994), and Gualtieri & Brignoli (2004); ( ) reported as augite in Carnevali et al. (1994), Gualtieri et al. (1999), and
5
6
Passaglia et al. (2005); ( ) measurement achieved using an X’Celerator detector; ( ) measurement achieved using a gas
proportional detector.
17
Conclusions
As planned in ACTION 2, in the first six months of project development the UniMORE unit carried out an indepth and comprehensive examination of the chemical and physical, as well as mineralogical characteristics
of chabazite-bearing zeolitite samples coming from several quarries in Central Italy (Grosseto, Viterbo, and
Rome Provinces), in order to select the most suitable raw material to be used throughout the entire
project. Besides the technological properties of the material, the final choice also took into account factors
such as the distance between the quarry and the site of the experimental field, which strongly affects
Carbon Footprint, the estimate, when available, of the total volume of exploitable geologic reserve and,
eventually, the prompt availability of a semi-finished ground product.
The K-rich, Na-poor zeolitite from the Piandirena quarry (Sorano, Gr) resulted to be a first-rate material for
the project purposes. It is in fact characterized by high zeolitic content (with dominant chabazite and very
subordinate phillipsite), as well as by high CEC value; in addition, our data and those found in literature
evidence a similar zeolite content at Sorano.
When compared to the other analyzed samples coming from quarries in Central Italy, the Sorano zeolitite
presents further valuable aspects that must be taken into account. In particular:
1) The Piandirena quarry is the closest to the town of Codigoro (Ferrara Province), where the experimental
field is located. This means lower CO2 emissions due to material transport, and consequent Carbon
Footprint reduction.
2) From a conservative estimate reported in a geologic study of the Sorano (Gr) zeolitite deposits, carried
out by Meggiolaro (2003) and committed by Verdi S.r.l. within the European Community Project “ZEOGYPBOARD” (Project n. GRD1-2000-25244), it results that the total volume of the geologic reserve for the
Piandirena quarry is of 6.500.000 m3. In 2003, when the geologic study was carried out, the already
exploited volume was of 1.830.000 m3. As reported by the quarrymen, from 2003 till now, about 200.000
m3 of zeolitite were dug out. According to these numbers, the currently available material in the quarry is
more than 4.450.000 m3.
3) In addition to the extractable zeolitite, the material available in dumps, whose technologic properties are
perfectly suitable for the purposes of the present project, must be also taken into account; in the 2003
geologic study, 650.000 m3 of this material were estimated. This aspect is of paramount concern from an
economic and environmental point of view, taking into account that the scrap material amounts to about
30% of quarry production and is currently unused.
4) The Piandirena quarry is equipped with a crushing and sieving apparatus, thus rendering available,
directly in the quarry and virtually without transport, a semi-finished ground product in two grain sizes (< 3
mm and 3-6 mm). The ground product is mainly made from the scrap material coming from broken bricks,
thus allowing to recycle an otherwise unused resource.
5) A further chemical analysis was performed on crystalline aggregates of chabazite picked up from the
sample from the Piandirena quarry. The results in weight percent oxides, along with the calculated
chemical formula, are reported in the following table:
18
Major elements
(wt% oxides)
Chemical formula
(apfu)
SiO2
52.33
Si
8.53
Al2O3
17.99
Al
3.46
Fe2O3
-
Fe
-
MgO
0.71
Mg
0.17
CaO
5.73
Ca
1.00
SrO
0.06
Sr
0.01
BaO
tr.
Ba
-
Na2O
0.43
Na
0.14
K2O
4.95
K
1.03
H2O
17.80
H2O
9.68
Total
100.00
As can be seen, the exchangeable cations are almost entirely represented by Ca and K, being Na, Mg, and Sr
quite negligible. The theoretical CEC value for the analyzed chabazite is 3.59 meq/g, of which 2.04 is due to
Ca, 1.05 to K, 0.35 to Mg, 0.14 to Na, and 0.01 to Sr. This is in agreement with the measured CEC values of
the Piandirena zeolitite (reported and discussed above), confirming that the whole rock CEC value is mainly
controlled by chabazite.
Aknowledgements
We aknowledge Verdi S.r.l. for giving us permission to consult the geologic study “The zeolite deposits of
Piandirena Sorano Central-Italy” (2003) by Dr. Vito Meggiolaro, and are grateful to Dr. Vito Meggiolaro for
searching for the original files in his archive and making them available to us.
References
Carnevali R., Gualtieri A., Passaglia E. (1994) Quantitative determination of zeolites component in Italian
pyroclastites by the Rietveld analysis of X-ray powder patterns. Materials Engineering (Modena, Italy)
(1994), 5(2), 211-21.
Donovan J.J. (1995) PROBRE: PC-based data acquisition and processing for electron microprobes. Advanced
MicroBeam, Inc., Vienna, Ohio.
Franzini M., Leoni L. & Saitta M. (1975) Revisione di una metodologia analitica per fluorescenza – X, basata
sulla correzione completa degli effetti di matrice. Rend. Soc. It. Min. Petr., 31(2), 365-378.
de’ Gennaro R., Cappelletti P., Cerri G., de’ Gennaro M., Dondi M., Langella A. (2004) Zeolitic tuffs as raw
materials for lightweight aggregate. Applied Clay Science 25 (2004) 71– 81
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11(2), 97-106.
19
Gualtieri A.F., Marchi E., Passaglia E. (1999) Zeolite content and cation exchange capacity of zeolite-rich
rocks. Studies in Surface Science and Catalysis, 125(Porous Materials in Environmentally Friendly
Processes), 707-713.
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33(2), 267-278.
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acque reflue e loro successivo impiego in agricoltura. Noi e l’ambiente, 52/53, 56-61.
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percolato da discarica e loro utilizzo in floricoltura. Noi e l’ambiente, 56/57, 34-37.
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ammendati con zeolitite a chabasite. Atti 3° Convegno AISSA “Il pianeta acqua nel continente
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20

Sub Action 2 1 - ZeoLIFE project

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