You are on page 1of 56

.

, -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Mineral Resources of
Greece
(-) (reserves-value) and
- Specifications-Uses
of Very High
Quality
Zeolitic Tuffs
. Anestis A. Filippidis
-
Professor of Mineralogy-Economic Geology
/
Head of the Laboratory of Geochemistry

Aristotle University of Thessaloniki
,
Faculty of Sciences, School of Geology
--
Department of Mineralogy-Petrology-Economic Geology 54124
54124 , . 2310-998468, 6972-778862
Thessaloniki, Greece, Tel. +30-2310-998468, Mobile 6972-778862
Email: anestis@geo.auth.gr
Email: anestis@geo.auth.gr
Website: http://anestis.webpages.auth.gr
Website: http://anestis.webpages.auth.gr
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


The hidden truth of our daily lives
Our needs
in mineral raw
materials

During her life,


, she will
, consume,
1380000 kg 1380000 kg of
, minerals,
metals and
. fuels.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


The hidden truth of our daily lives
The construction of a
, common house,
260 requires
260 tons of industrial
minerals and rocks
1 kg Al
4 kg

The production
of 1 kg of Al
requires 4 kg of
bauxite
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


The hidden truth of our daily lives
A common car contains
15000 15000 parts and elements
that are produced from mineral raw materials
100-150 kg 100-150 kg
(, , , ) industrial minerals (glasses, tires, plastics, etc
1 1 ton
(Al, Fe, Ni, Cr, Mn, ) of metals (Al, Fe, Ni, Cr, Mn, )
/ Hematite / Galena / Possolan
/ Natural zeolite
Perlite


/ Quartz
Chalcopyrite / Mica
Magnetite / Calcite

/ Talc / Gypsum
/ Malachite Wollastonite

/ Feldspar
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


The hidden truth of our daily lives
1 500-600 KWh

4/
10 /

4000 /

1 ton lignite produces 500-600 KWh

A 4/member family requires


10 tons of lignite / year
or
4000 barrels of oil / year
for its electricity needs
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

,
Mineral resource, is a concentration or occurrence
,
of material with financial interest,
, ,
in such form, quality and quantity, that there are
.
reasonable expectations for final extraction.
:
Mineral Resources:

Energy mineral raw materials
(, , , , )
(coals, oil, natural gas, uranium, geothermics, etc)

Metallic Mineral deposits
(Al, Pb, Zn, Ni, Fe, Cr, Mn, Cu, Au, Ag, )
(Al, Pb, Zn, Ni, Fe, Cr, Mn, Cu, Au, Ag, etc)
&
Industrial Minerals & Rocks
(, , , , ,)
(kaolin, marbles, perlite, zeolites, gemstones, etc)
PERC (
The PERC code (Pan-European Reserves and Resources
, PERC: Pan-European Reserves and
Reporting Committee) applies,
Resources Reporting Committee) ,
numerous, specific and strict requirements,
, ,
for characterizing the resources / reserves.
/ .
To characterize the mineral resources / reserves,
/ ,
among others, are seriously considered,
, ,
the measured quantitative and qualitative data,
,
the exploitability of the reserves, the extracting and
,
processing costs, the international markets, the legal,
, , ,
environmental, social and governmental factors.
, .
Classification of the mineral resources (reserves):
():
Inferred Indicated (Probable) Measured (Proven).
() ().
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

, -
Prinos oil platform, Kavala-Thasos


Ptolemais Lignite

Energy Mineral Raw Materials of Greece


( & 2011, 2013, Tsirambides & Filippidis 2012) ( & 2011, 2013, Tsirambides & Filippidis 2012)
. . , - Mineral Gross value Gross value of exploi-
Reserves
(. ) (. ) resource (million ) ting today (million )
Lignite Proven
268.000 2.160 268,000 2,160
+ 6.700.000 . . +Peat 6,700,000 Th. ton.
Indicated
408.700 - Natural gas 408,700 -
3,5 . m3 3.5 trillion m3
Indicated
685.000 75 Oil 685,000 75
10 . 10 billion barrels
Uranium Indicated
150 - 150 -
U3O8 1,80 . . U3O8 1.80 Th. ton.
> 1.000 Mwt 900.000 80 Geothermics Proven >1,000 Mwt 900,000 80
2.261.850 2.315 Total 2,261,850 2,315
0,10% Exploiting today 0.10%
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Pyrite Chromite
Olympias Vourinos
Chalkidiki Kozani


Ag-




Bauxite
Ag-Galena
Distomo
Olumpias
Viotia
Chalkidiki

Metallic Mineral Resources of Greece


( & 2011,2013, Tsirambides & Filippidis 2012) ( & 2011,2013, Tsirambides & Filippidis 2012)
. . , - Reserves Gross value Gross value, of exploiting
Mineral resource
. . (. ) (. ) Thousand tones (million ) today (million )
(Al) 2.500 4.040 38 Aluminium (Al) Proven 2,500 4,040 38
+ - Lead + Zinc
3.125 5.184 354 Proven 3,125 5,184 354
(Pb+Zn) (Pb+Zn)
(Ni) 1.392 19.965 63 Nickel (Ni) Proven 1,392 19,965 63
(Cr) 1.200 2.552 - Chromium (Cr) Proven 1,200 2,552 -
(Mn) 2.250 5.220 - Manganese (Mn) Proven 2,250 5,220 -
(Cu) 1.943 12.431 - Copper (Cu) Proven 1,943 12,431 -
19,37 Proven 19.37
(Au) 26.556 - Gold (Au) 26,556 -
. million ounces
131,60 Proven 131.60
(Ag) 3.454 - Silver (Ag) 3,454 -
. million ounces
79.402 455 Total 79,402 455
0,57% Exploiting today 0.57%
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

& Industrial Minerals & Rocks


of Greece
(Filippidis 1993-2016, 2001-2016, (Filippidis 1993-2016, 2001-2016,
& 2011, 2013, Tsirambides & Filippidis 2012) & 2011, 2013, Tsirambides & Filippidis 2012)
. . , - Reserves Gross Gross value, of
Mineral resource
. . (. ) (. ) Thousand tones value(m. ) exploiting today (m. )
1. >3.000 300,0 1.Aggregates Proven Inexhaustible >3,000 300.0
2. 13.000 260 0,6 2.Attapulgite Proven 13,000 260 0.6
3. 100.000 3.500 43,8 3.Bentonite Proven 100,000 3,500 43.8
4. >270 27,0 4.Carbonates Proven Inexhaustible >270 27.0
5. 80.000 1.200 0,4 5.Feldspars Proven 80,000 1,200 0.4
6. 6.Gypsum
350.000 2.100 2,8 Proven 350,000 2,100 2.8
Anhydrite
7. 20.000 80 1,0 7.Halite Proven 20,000 80 1.0
8. 4.000 160 0,7 8.Huntite Proven 4,000 160 0.7
9. 9.Kaolin
50.000 750 0,6 Proven 50,000 750 0.6
Clay
10. 280.000 9.800 14,0 10.Magnesite Proven 280,000 9,800 14.0
11. >5.000 500,0 11.Marbles Proven Inexhaustible >5,000 500.0
12. 12.Olivine
50.000 500 0,4 Proven 50,000 500 0.4
Dunite
13. 1.200.000 12.000 12,4 13.Perlite Proven 1,200,000 12,000 12.4
14. 14.Pumice
400.000

4.000 9,5 Proven 400,000 4,000 9.5
Pozzolan

15. 15.Quartz
5.000 100 0,8 Proven 5,000 100 0.8
Opal
16. 100.000 2.500 - 16.Diatomite Proven 100,000 2,500 -
17. 1.300 40 - Zeolitic tuff 17.Garnet Indicated 1,300 40 -
18. 650 20 - Ntrista Stream 18.Graphite Indicated 650 20 -
19. 800 20 - Petrota, Evros 19.Micas Indicated 800 20 -
20. 500 10 - 20.Phosphorites Indicated 500 10 -
21. 1.000 20 - 21.Talc Proven 1,000 20 -
22. 500 20 - 22.Vermiculite Proven 500 20 -
23. 500 20 - 23.Wollastonite Indicated 500 20 -
24. 600.000 18.000 - 24.Zeolites Proven 600,000 18,000 -
63.370 914,0 Total 63,370 914.0
1,44% Exploiting today 1.44%
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


(Filippidis 1993-2016, 2001-2016,
& 2011, 2013, Tsirambides & Filippidis 2012)
. ,
.
-


(. )
O
(. ) (%)
-
O
G
: , , -
O 2.261.850 2.315 0,10
G
: , , U -
G
O
- 79.402 455 0,57
: Al,Pb,Zn,Ni,Cr,Mn,Cu,Au,Ag G
& () O-
: 16 , , , .. O
G 63.370 914 1,44
-
: 8 , , , ... G
2.404.622 3.684 0,15

Mineral Resources of Greece


(Filippidis 1993-2016, 2001-2016,
& 2011, 2013, Tsirambides & Filippidis 2012)
Gross value, of
Gross Exploiting
exploiting
value today
today
(million ) (%)
O
(million )
Energy Mineral Raw Materials -
O
G
Proven: Lignite, peat, geothermics - 2,261,850 2,315 0.10
O
G
Indicated: Oil, gas, U -
G
O
Metallic Mineral Deposits - 79,402 455 0.57
Proven: Al,Pb,Zn,Ni,Cr,Mn,Cu,Au,Ag G
O
Industrial Minerals & Rocks (IMR) -
Proven: 16 IMR, Aggregates, marbles, .. O
G 63,370 914 1.44
-
Indicated: 8 IMR, Diatomite, zeolites, .. G

Grand total 2,404,622 3,684 0.15


. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


No extortionate exploitation Use sparingly Recycling Environmental Legislation Restoration




Bad
example

Quarry
restoration
Lykavitos
theater, Attiki

Good Quarry
Example restoration
Gerakini Athletic
Chalkidiki center
Cholargos
Attiki
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

( ~10 ) Zeolitic tuff (contains ~10 minerals)


= = Rock
# Natural zeolites # Synthetic zeolites
( ) (very high cost)

The zeolitic volcaniclastic rock deposit,


, corresponds to a rock which contains high
, amounts of one or more,
67 . from the 67 different phases of zeolites.
, The zeolite with the numerous applications, is the
-HEU (-). HEU-type zeolite (clinoptilolite-heulandite).

, , Considering among others,


* 651/2013, *EU Regulation No 651/2013,
86/278//1986 & 98/83//1998, EU Directives 278/EEC 1986 and 98/83/EC/1998,
* , *the high toxicity in animals and humans,
SiO2 of fibrous zeolites and crystalline silica
(e.g., Davis 1993, Driscoll 1993; Ross et al. 1993, (e.g., Davis 1993, Driscoll 1993; Ross et al. 1993,
& 2012, 2015, Filippidis 2013, 2014, 2015, & 2012,2015, Filippidis 2013, 2014, 2015,
2014, 2015, .. 2014, 2014, 2015, .. 2014,
& 2016, Filippidis et al. 2016), & 2016, Filippidis et al. 2016),
* , *the pozzolanic activity of minerals,
* , *the bioavailability of elements,
* & () *the trace elements and radionuclides
, (radioactivity) of zeolitic tuffs,

. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

.. , .. considering,
* *the high performance in numerous applications of very h
(89% ) igh quality zeolitic tuff (89% Clinoptilolite)
(e.g., .. 1995-2014, Filippidis et al. 1996-2016, (e.g., .. 1995-2014, Filippidis et al. 1996-2016,
2001-2016, Filippidis & Kantiranis 2005, 2007, 2001-2016, Filippidis & Kantiranis 2005, 2007,
Filippidis 2008-2016). Filippidis 2008-2016).

* - *the negative-zero performance


( ), in greenhouse crops (lettuce and peppers),
(), in the field (maize),
in the removal of metals from wastewater
, and drinking water, due to the addition of low quality
(40% ) zeolitic tuff (40% clinoptilolite)
( 2008, & 2009), ( 2008, & 2009),

*, *that, the low quality zeolitic tuff


(70% ), (70% clinoptilolite), proved to be insufficient for
(Mazeikiene et al. 2008) nitrate retention (Mazeikiene et al. 2008)
* - *the performance-yield and the cost
, in all type of uses,

it is very important to emphasize the quality


, characteristics of the zeolitic tuffs,
. in relation to different uses.
- The specifications for the various uses-applications
-HEU of HEU-type (clinoptilolite-heulandite)
(-) : zeolitic tuffs are:
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Erionite Mordenite Roggianite Mazzite


Gottardi
& Galli
1985

(1) (1st)
, The zeolitic tuff, for all uses, must be
( 651/2013) free of fibres (EU Regulation No 651/2013) and
consequently free of fibrous zeolites and
( ). other fibrous minerals (tiny needles).

(.., , , The presence of fibrous zeolites (e.g., erionite, mordenite,


, , , , , roggianite, mazzite, scolecite, mesolite, natrolite,
) ferrierite) is inhibitory for any use
. of the zeolitic tuffs.

( , The fibrous zeolites (mainly erionite, mordenite and to a


, ), lesser extent roggianite, mazzite), in humans
, , and animals, inhaled or injected or swallowed,
, . are toxic, carcinogenic and highly pathogenic.
(e.g., Davis 1993, Driscoll 1993; Ross et al. 1993, & 2012, 2015, Filippidis 2013, 2014, 2015,
2014, 2015, .. 2014, & 2016, Filippidis et al. 2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Q:
Quartz in clinoptilolite-containing zeolitic tuff

(e.g., Tsirambides et al. 1988-1993, Kirov et al. 1989-1990, Filippidis 1993-2015,


.. 1995-2014, Filippidis et al. 1995-2016, 2001-2016,
Kantiranis et al, 2002-2011)

(2) (2nd)
, The zeolitic tuff must be free of quartz, for
( ), , Use (in powder form), as feed additive for all animal
( 651/2013) Species (EU Regulation No 651/2013) and
, . consequently for humans as nutrition supplement.

The same applies to the use as livestock floor materials,


, in case the animals are used to consume materials
. from the floor.

( , The fibrous zeolites (mainly erionite, mordenite and to


, ), a lesser extent roggianite, mazzite), as well as
SiO2 ( ) the crystalline SiO2-phases (the minerals)
, quartz, cristobalite, tridymite
( ), (tiny insoluble axes),
, , in humans and animals, inhaled or injected or swallowed,
. are toxic, carcinogenic and highly pathogenic.

(e.g., Davis 1993, Driscoll 1993; Ross et al. 1993, & 2012, 2015, Filippidis 2013, 2014, 2015,
2014, 2015, .. 2014, & 2016, Filippidis et al. 2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

cpt: , ce: ( )
(e.g., Tsirambides et al. 1988-1993, Kirov et al. 1989-1990, Filippidis 1993-2015, ..
1995-2014, Filippidis et al. 1995-2016, 2001-2016, Kantiranis et al, 2002-2011)

cpt: Tabular crystals of Clinoptilolite, ce: Celadonite (Illite group)

(3) (3rd )
, For all uses, the content of the
, clinoptilolite in the zeolitic tuff,
80 %. should be 80 wt%

M: , AF: -, PL:

(e.g., Tsirambides et al. 1988-1993, Kirov et al. 1989-1990, Filippidis 1993-2015,


.. 1995-2014, Filippidis et al. 1995-2016, 2001-2016,
Kantiranis et al, 2002-2011)

M: Mica, AF: Alkali-feldspar, PL: Plagioclase

(4) (4th)
The content of the clay minerals in the
, 20 %. zeolitic tuff, should be 20 wt%.

( Particular care is required (zero or very low content)


) for the swelling clay minerals
with pozzolanic activity
( ), (equivalent in action to the cement),
, the above do not apply for uses, as material in the
. construction industry and as additive for cement production.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

(5) (5th)
The zeolitic tuff should not be
, burdened or contaminated with major elements,
() trace elements and radionuclides (radioactivity)
, and their concentrations, according to

* , , *the World, European and Greek legislation,


should not exceed the
() Maximum Allowable Concentrations (MAC)
of trace elements in agricultural soils
( 86/278//1986, (EU Directive 86/278/EEC 1986,
80568/4225/1991), Ministerial Decision 80568/4225/1991),

* *the total worldwide average annual effective


radiation dose from natural sources
(2,4 mSv/, UNSCEAR 2000), (2.4 mSv/year, UNSCEAR 2000),
and generally should not be enriched
compared to the average values of rocks
(Mason & Moore 1982). and the crustal average (Mason & Moore 1982).

* , *For consumption by animals and humans,


caution is needed to the limit values of trace elements
and the total indicative dose of radioactivity
(0,10 mSv/) (0.10 mSv/year) of water intended for human
( 98/83//1998). consumption (EU Directive 98/83/EC/1998).

(e.g., & 2012, Filippidis 2013-2016, & 2016, Filippidis et al. 2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

(6) (6th)
- The bioavailability and seepage of dangerous-harmful metals,
, , trace elements and chemical compounds of the zeolitic tuff,
. should be zero or extremely low.

, The metals and trace elements, should be located within the


() crystal structure of the zeolite (absorption) rather than the surface
(, ). of the zeolite crystals (adsorption, surface precipitation).

, The very high quality zeolitic tuffs, selectively sorb and fixate, the
, - -, dangerous-harmful metals-trace elements, with strong chemical
, bonds and do not allow them to be transferred to the plants, while
, the beneficial chemical elements are available to the plants, since
. the zeolitic tuff selectively sorb them with loose chemical bond.

(7) (7th)
The main exchangeable cations of the clinoptilolite
, , Ca, Mg Na. contained in the zeolitic tuff, should be K, Ca, Mg and Na.

(8) (8th)
( ) The sorption-uptake ability (ion exchange capacity)
, >175 meq/100g. of the zeolitic tuff, should be >175 meq/100g.

(9) (9th)
, The granulations of the zeolitic tuff for different uses,
shards should consider the size of the shards and
. the type of application.

(10) (10th)
, The correlation of the cost, the economic and environmental
, . benefits, always should seriously be considered.

(e.g., & 2012, Filippidis 2013-2016, & 2016, Filippidis et al. 2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

/- Micro/nano-pores in a network of
10- 8- , 10-member and 8-member rings of
7,53,1 (V=23,25), dimensions 7.53.1 (V=23.25),
4,63,6 (V=16,56) & 4.63.6 (V=16.56) &
4,72,8 (V=13,16) 4.72.8 (V=13.16)

Lewis (-)
Lewis (-) basic active sites and
Broensted (+)
Brnsted (+) acidic active sites
in the surface of the
clinoptilolite crystals

- Meso-pores between the crystals


, of the clinoptilolite,
- Macro-pores of the zeolitic tuff
(Baerlocher et al. 2001, Mitchell et al. 2012)

Even if the zeolitic tuff fulfill all the


, , mineralogical, chemical, morphological and
, radiological specifications,

particular care is needed for those who take


, medicines, because the zeolitic tuff as a material with
, , high adsorption capacity, can bind,
inactivate and remove the beneficial
, medicine from the human body,
. with consequent harm.
(e.g., Filippidis 2013-2016, & 2016, Filippidis et al. 2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

he color
of the zeolitic tuff
is irrelevant to the quality
20-25 . : 3-5 . 20-25 mil. years ago: 3-5 volcanic activities.
. Volcanic centers in NE Bulgaria and Thrace.
, Acid volcanism, alteration of volcanic glass
. to different types of zeolites.
T, P, pH, , .., Depending on the T, P, pH, salinity, etc.,
-- Sedimentation basins-diagenesis-mixing of clastic materials
Volcaniclastic tuffs of
10-100 ( 1 cm 10 m) 10-100 layers (thickness 1 cm 10 m)
Each layer has different mineralogical and chemical composition
-- Tectonics-fractures-weathering removed vertically and
. horizontally the tuffs to new sites/locations.
Neighboring sites/locations/layers
& show differences in mineralogy & chemistry
. and different quality characteristics.
74%

Gkazomilos Ntrista stream Clinoptilolite Vertical site
20 m 20 m

58% Average
(24 ) (24 layers)
Clinoptilolite = 89% = 89%
Clinoptilolite

95%
: Variation:
74-95% 74-95%
Clinoptilolite
Filippidis 1986 (e.g., Tsirambides et al. 1988-1993, Kirov et al. 1989-1990, Filippidis 1993-2015, .. 1995-2014,
Filippidis et al. 1995-2016, 2001-2016, Kantiranis et al, 2002-2011)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

( ) Greek Zeolitic Tuffs (Natural Zeolites)


68 , 9 In 68 locations of zeolitic rocks in Greece, 9 species of zeolites were
(-, , , , found (clinoptilolite-heulandite, mordenite, erionite, scolesite,
, , , , ), analcime, laumontite, stilbite, phillipsite, chabazite),
33 33 locations contain fibrous zeolite
(, , ), (mordenite, erionite, scolecite),
31 8-70% , 3 74-77% 31 locations contain 8-70% zeolite, 3 locations 74-77% zeolite and
specific layers of zeolitic tuffs in Ntrista stream location
( ) 89% , (Petrota, Evros) contains 89% clinoptilolite,
(). named the Hellenic Natural Zeolite (HENAZE).

( According to European and Greek legislation (EU regulations


651/2013), , 651/2013), all Greek zeolitic rocks, since they contain
, quartz fibrous zeolites cristobalite tridymite,
are unsuitable and dangerous for consumption
( ) of all animal species (feed additives)
( ). and consequently of humans (as nutrition supplements).
(e.g., Tsirambides et al. 1988-1993, Kirov et al. 1989-1990, Filippidis 1993-2015, .. 1995-2014,
Filippidis et al. 1995-2016, 2001-2016, Kantiranis et al, 2002-2011)

Greek Number of Locations


/ Zeolitic Rocks Zeolite content With With Quartz
( ) 74, 74, - (Natural Zeolites) 74, 74, HENAZE fibrous Cristobalite To-
- 8-70% 77% 89% Prefecture-Island 8-70% 77% 89% zeolites Tridymite tal
7 - - 2 9 9 Samos 7 - - 2 9 9
: , Cyclades: ,
, , 2 - - 7 9 9 Milos, Polyegos, 2 - - 7 9 9
Santorini
, , Zakynthos, Lefkada,
3 - - - 3 3 3 - - - 3 3
Kilkis
2 - - 7 9 9 Rhodopi 2 - - 7 9 9
17 3 1 17 38 38 Evros 17 3 1 17 38 38
31 3 1 33 68 68 Total 31 3 1 33 68 68
46% 4% 1% 49% 100% 46% 4% 1% 49% 100%
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Low Quality Zeolitic Tuffs


, The low quality zeolitic tuffs, provided that
, are free of fibrous zeolites, other fibrous minerals and
(), are not burdened with radionuclides (radioactivity),
can be used as dimension
. and decorative stones.

As dimension stones in buildings creates a cool


, environment in the summer and warm in winter, while in
. the stables reduces ammonia and malodor.
Metaxades Evros
(e.g.,Tsirambides et al.1988-1993, Filippidis 1993, Savin et al.1993, Koutles et al.1995, ..1995-1997,
2001-2015, Tzamos et al.2010-2012, Filippidis et al.2007-2016


..

1910
Dimension stones of low
quality zeolitic tuffs
.. Terzoglou
House
1910




1926 1939

1975
KARAGGELAKIS Church
AGGELAKIS Prophet
Coffe-house Elias City Hall
1926 1939 1975
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Specific layers of zeolitic tuffs


( ) in Ntrista stream location (Petrota, Evros)
89% , contains 89% clinoptilolite, named the
(), Hellenic Natural Zeolite (HENAZE),
, is of very high quality with numerous industrial,
, . environmental, agricultural and water applications.
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
/ The rock / The granulates
/ Powder

-: Shards, - - - / The micro-scale: Shards, Micro- Meso- Macro-pores


- - Shards (~ 0.1-2.0 mm) Shard
Z =
Clinoptilolite - -
Q =
Quartz
Cl = Meso- Macro-
Clay minerals pore pore

/ Grain-size distribution of HENAZE granulates 3 - < 25 .


/ Fraction (mm) : Broensted (+)
<1.5- <1- <0.5- <0.25- <0.125- Lewis (-).
<0.063 Total Within the crystal 3 micro-pores < 25 .
1 0.5 0.25 0.125 0.063
<1.5 mm 4% 14 % 17 % 19 % 21 % 25 % 100 wt.% On the surface of the crystal: Broensted (+) acid active sites
<0.5 mm - - 7% 27 % 31 % 35 % 100 wt.% and Lewis (-) basic active sites.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

* **
ineralogical composition* and sorption ability** of HENAZE IGME
/ Clinoptilolite 89 wt.% .. 2008
+ A (, , ) +
3
Mica + Clay minerals (smectite, illite, celadonite) Clinoptilolite + Mordenite
/ Quartz 3 = 53 wt.%
/ Cristobalite Tridymite 2
(A- + )
3
Feldspars (Alkali-feldspar + Plagioclase)
/ Total 100 Sorption ability
/ Sorption ability 187 (meq/100g) = 80 meq/100g
*) X-Ray Diffraction **) AMAS

SEM
(cpt)
( ~5-50 m)
(ce) ( ) (M)
: (PL) , (AF) -, (Q)
Microphotograph SEM
(cpt) Clinoptilolite Microphotograph of polarized microscope
(typical tabular crystals ~5-50 m) (M) Mica flakes
(ce) Celadonite (illite group) Angular crystals: (PL) Plagioclase, (AF) Alkali-Feldspar, (Q) Quartz
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

/ The chemistry of minerals in the HENAZE


.- Chemical formulae of the minerals in HENAZE
wt.%
Clinoptilolite Mica Clays Alkali-feldspar Plagioclase
SiO2 66.20 34.63 55.74 66.19 57.20
TiO2 0.02 5.45 0.01 0.09 0.01 Clinoptilolite
Al2O3 12.12 15.47 15.84 18.68 27.20 Ca1.8K1.1Mg0.7Na0.5Al6.4Si29.6O72.21H2O
Fe2O3tot 0.14 - 9.10 - -
FeOtot - 17.84 - 0.02 0.01

MnO 0.03 0.97 0.08 0.01 0.01
MgO 1.01 12.37 1.94 0.01 0.01
Mica
CaO 3.80 0.04 1.55 0.38 9.46 Mg1.4Fe1.1K0.8Na0.1Mn0.1Ti0.3Al1.4Si2.6O10(OH)2
Na2O 0.58 0.82 0.01 4.20 5.92
K2O 1.88 8.20 5.22 10.48 0.65
H2O 14.22 4.21 10.51 - - Clay minerals
Total 100.00 100.00 100.00 100.06 100.47 Fe1.0K0.9Mg0.4Ca0.2Al2.4(Al0.2Si7.8)O20(OH)42.9H2O
(O) / Atoms per oxygen (O)
72 (O) 12 (O) 24 (O) 8 (O) 8 (O)
Si 29.5549 2.6121 7.7745 2.9960 2.5590
, ,
Al (IV) 6.3772 1.3752 0.2255 0.9965 1.4341 Quartz, Cristobalite, Tridymite
Al (VI) - - 2.3784 - - SiO2
Ti 0.0067 0.3091 0.0010 0.0031 0.0003
Fe3+ 0.0157 - 0.9551 - - ()
Fe 2+ - 1.1253 - 0.0008 0.0004 Alkali-feldspar (sanidine)
Mn 0.0113 0.0620 0.0095 0.0004 0.0004
Mg 0.6721 1.3907 0.4033 0.0007 0.0007
K0.6Na0.4Al1.0Si3.0O8
Ca 1.8177 0.0032 0.2316 0.0184 0.4534
Na 0.5020 0.1199 0.0027 0.3686 0.5135 ()
K 1.0707 0.7890 0.9288 0.6052 0.0371 Plagioclase (andesine)
OH - 2.1182 4.0006 - - Na0.5Ca0.5Al1.4Si2.6O8
H2O 21.1735 - 2.8888 - -
/ Cell parameters of the Clinoptilolite (e.g., 2002-2016, &
a () b () c () V (3) 2002, .. 2006-2016, Filippidis et al. 2007-
17.663 17.917 7.406 2099.640 116o38 2016, Filippidis 2007-2016).
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

SEM-EDS (), The combined methods of SEM-EDS (microanalyses),


450o C 8 thermal treatment at 450o C for 8 hours and
(XRD) (Kantiranis et al. 2006), X-Ray Diffraction (XRD) (Kantiranis et al. 2006),
-HEU , revealed that the HEU-type zeolite in the HENAZE,
presents characteristics of group I zeolite
() 2 (clinoptilolite) in 2 samples and
II ( ) 1 . of group II (intermediate heulandite) in 1 sample.
( ) *
Chemical composition (major elements) of the HENAZE*
SiO2 66.79 MnO 0.03 K2O 2.37
TiO2 0.17 MgO 0.92 P2O5 0.02
Al2O3 12.07 CaO 2.71 L.O.I. 12.39
Fe2O3 tot 1.22 Na2O 1.23 Total 99.92
*(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)


-


ppm= *
(kg/ha/) (%)
mg/kg HENAZE* Different Limit values in
Crustal Maximum Allowable Limit values in Limit values for amounts that may World soil Bioavailability
rocks water for human
Average Concentrations (MAC) sewage sludge for be added to cultivated soils average in soils (%)
consumption
in agricultural soils use in agriculture (Kg/ha/year)
Cd <0.5 0.2 0.03-0.15 13 20-40 0.15 0.41 0.005 0.6
Cr 23 100 11-114 50 150 - - 59.5 0.05 <0.1
Cu 2 55 4-110 50 140 1000-1750 12 38.9 2 0.3
Hg 0.006 0.8 0.1-0.4 1 1.5 16-25 0.1 0.07 0.001 -
Ni 4 75 1-76 30 75 300-400 3 29 0.02 <0.1
Pb 41 13 7.8-48 50 300 750-1200 15 27 0.01 <0.1
Zn 46 70 16-95 150 300 2500-4000 30 70 0.1
Mason & Moore 1986/278/, Kabata- Petrotou et al.
1982 EU Directive 1986/278/EEC Pendias 1998/83/ 2010,
.. 80568/4225/91 ( 641//7-08-1991) 2011 EU Directive Skordas et al.
1998/83/EC 2013
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

/ Trace element contents of the HENAZE


- . - .
. .
ppm ppm
Met- Det. HENAZE Crustal Different World soil Met- Det. HENAZE Crustal Different World soil
hod limit average rocks average hod limit average rocks average
Ag FM 0.5 <0.5 0.07 0.07-0.08 0.13 Mo FM 2 <2 1.5 0.2-6.5 1.1
As IN 2 4 1,8 0,5-13 6,83 Nb FM 0.2 15.0 20 0.3-24 12
Au IN 0.005 <0.005 0.004 0.004 0.003 Nd FM 0.1 19.9 28 6.2-55 26
Ba FI 3 172 425 10-1230 460 Ni TD 1 4 75 1-76 29
Be FI 1 6 2.8 0.8-3 1.34 Pb FM 5 41 13 7-48 27
Bi FM 0.1 0.2 0.2 0.05-0.4 0.42 Pr FM 0.01 7.08 8.2 1.5-19 7
Br IN 1 <1 2.5 0.4-6.2 10 Rb FM 1 150 90 3-220 68
Cd TD 0.5 <0.5 0.2 0.03-0.3 0.41 Sb FM 0.2 0.2 0.2 0.2-1.5 0.67
Ce FM 0.1 64.4 60 10-170 56.7 Sc IN 0.1 3.0 22 1-35 11.7
Co FM 1 8 25 0.1-47 11.3 Se IN 3 <3 0.05 0.007-0.6 0.44
Cr IN 1 23 100 11-114 59.5 Sm FM 0.01 3.52 6.0 3.6-8.3 4.6
Cs FM 0.1 8.9 3 0.9-5 5.06 Sn FM 1 4 2 2-6 2.5
Cu TD 1 2 55 4-110 38.9 Sr FI 2 1104 375 20-610 175
Dy FM 0.01 3.44 3.0 1.1-4.3 3.6 Ta FM 0.01 1.13 2 0.5-2 1.39
Er FM 0.01 2.29 2.8 0.7-2.8 2.2 Tb FM 0.01 0.24 0.9 0.2-0.9 0.63
Eu FM 0.005 0.294 1.2 0.3-1.3 1.4 Th FM 0.1 30.5 7.2 1.7-50 9.2
Ga FM 1 14 15 4-20 15.2 Tl FM 0.05 1.29 0.5 0.11-1.2 0.5
Gd FM 0.01 3.12 5.4 1.4-5.4 3.9 Tm FM 0.005 0.367 0.5 0.1-0.5 0.37
Ge FM 0.5 1.4 1.5 0.2-1.6 2.0 U FM 0.01 8.56 1.8 0.35-3.7 3.0
Hf FM 0.1 4.3 3 0.3-5.2 6.4 V FI 5 17 135 17-264 129
Hg FA 0.005 0.006 0.08 0.1-0.4 0.07 W FM 0.5 3.7 1.5 0.4-1.8 1.7
Ho FM 0.01 0.72 1.2 0.3-1.2 0.72 Y FM 0.5 20.4 33 6.4-33 23
In FM 0.1 <0.1 0.1 0.02-0.1 0.06 Yb FM 0.01 2.52 3.4 0.7-3.4 2.6
Ir IN 0.005 <0.005 0.001 0-0.003 - Zn TD 1 46 70 16-95 70
La FM 0.1 37.1 30 6.3-101 27 Zr FI 2 137 165 19-220 267
Lu FM 0.002 0.409 0.5 0.19-0.6 0.37 (FM) FUS-MS: Fusion Mass Spectrometry, FA: Fire Assay
(FI)FUS-ICP:Fusion Inductively Coupled Plasma, (IN)INAA:Instrumental Neutron Activation Analysis, (TD)TD-ICP:Total Digestion ICP
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


Leachability of elements from the HENAZE

Initial concentration Leachate Leachability
(mg/kg) (mg/L) (%)
Mg 6575 0 0
Ca 23514 0 0
Na 5564 2.60 0.0467
K 15359 0.30 0.0020
-
Physico-chemical properties of HENAZE
( )
187 (meq/100g)
mmonia ion exchange capacity (sorption ability)

1.70 g/cm3
Bulk density

2.05 g/cm3
Real density

23.0 MPa
Uniaxial compressive strength

28.4 m2/g
Specific surface area
Radiation dose

Worldwide average annual effective radiation dose from natural sources
(UNSCEAR 2000) (mSv/y) (mSv/y)
2.4 0.17
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

, & Agricultural, Industrial & Environmental Applications



100% 85% +15%

Root system of Root system of


cucumber plant cucumber plant
100% soil 85% soil+15% HENAZE

H The addition of HENAZE in agricultural soils


* *Improves the physicochemical and nutritious abilities of the soils
* *Reinforces the root-system of the plants
* *Reduces the diseases of the plants root-system
* *Reduces the losses of the plants
* , , *Sorbs and becomes a carrier of fertilizers, herbicides,
pesticides and other organic substances
* *Stores and offers gradually the water to the plants
* , *Offers gradually to the plants nutrients and fertilizers
* *Reduces the leaching of nutrients and fertilizers
( ) (better efficiency of fertilizers)
* , *Traps harmful metals and components, preventing them
to be transferred to the plants and thus protecting the plants
and the quality of agricultural products
* *Sorbs and removes cyanobacteria
* pH *Adjusts to neutral the pH of the soils
* *Improves contaminated soils
* *Increases the production of agricultural products
* *Prevents the leaching of harmful components
, by the rain water, thus protecting the
, quality of soils, surface and ground waters
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

pH pH control of soils to neutral


(500 kg/) by HENAZE (500 kg/acre)
pH pH pH Initial soil Soil pH Soil pH
16 5 pH after 16 days after 5 years
pH 3,8 4,0 5,6 6,0 5,8 6,2 pH 3.8 4.0 5.6 6.0 5.8 6.2
47 50 % 53 55 % Improvement 47 50 % 53 55 %

Reclamation of contaminated soils


, HENAZE, selectively binds and fixate
- -, the dangerous-harmful metals-trace elements,
with strong chemical bonds
, and does not allow them to be transferred to the plants,
, while the beneficial chemical elements,
, are available to the plant,
because they are selectively bound
. by loose chemical bonds.

Reclamation of contaminated soils


Hg Seepage reduction HENAZE Hg reduction
HENAZE
500 (%) 600 (%) (%) 600 (%)
500 kg/acre
kg/. Cd Cs Pb Zn Ni kg/. Cd Cs Pb Zn Ni kg/acre Shoots Roots
Contaminated
33 39 44 52 60 77 53 33 39 44 52 60 Trifolium 77 53
soil
Mine
43 - 52 71 - 78 47 43 - 52 71 - Grass 78 47
land
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Quality improvement of agricultural products


Quality Production
Improvement
characteristics without with
(%)
(%) of tomato HENAZE HENAZE
Soluble solid
4,20 4,35 4 4.20 4.35 4
(%) components (%)
C Vitamin C
6,81 8,61 26 6.81 8.61 26
(mg/100g) (mg/100g)
Firmness
0,619 0,906 46 0.619 0.906 46
(kg) (kg)
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)

Decrease of Nitrate Load in the Leachates of Agricultural Soils


( ) by HENAZE (protection of the quality of groundwaters)
Start Intermediate End
5,5 8 10 5.5 th 8 th 10th
week week week
A: AS:
894 mg/L 162 mg/L 81 mg/L 894 mg/L 162 mg/L 81 mg/L
Agricultural Soil
+0,2% AS+0.2% HENAZE
38% 26% 2% 38% 26% 2%
500 kg /. 500 kg HENAZE/acre
+0,4% AS+0.4% HENAZE
47% 50% 81% 47% 50% 81%
1000 kg /. 1000 kg HENAZE/acre
+0,6% AS+0.6% HENAZE
49% 55% 86% 49% 55% 86%
1500 kg /. 1500 kg HENAZE/acre
(e.g., 2016, Hatzigiannakis et al. 2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Increase of production by addition of


(200-600 kg/.) HENAZE (200-600 kg/acre) in agricultural soils
Average
() Product (area)
() (%) (range) (%)
( ) 95 Barley (Gefyra Thessaloniki) 95
() 94 Potato (Gefyra) 94
( 63 Grape (Agios Athanasios 63
& ) (25, 48, 65, 66, 73, 99) Thessaloniki & Gefyra) (25, 48, 65, 66, 73, 99)
() 50 Maize (Gefyra) 50
49 49
( & ) Tomato (Aspro Pella & Gefyra)
(11, 39, 48, 50, 52, 96)
(11, 39, 48, 50, 52, 96)
( ) 45 Actinides (Livadochori Serres) 45
( & ) 43 (29, 57) Wheat (Gefyra & Livadochori) 43 (29, 57)
( ) 35 (33, 37) Apples (Naousa Imathia) 35 (33, 37)
( ) 34 Rice (Chalastra Thessaloniki) 34
() 33 Garlic (Gefyra) 33
() 33 (31, 35) Peaches (Naousa) 33 (31, 35)
() 17 Cotton (Livadochori) 17
Florescence of carnation
33 (25, 40)
33 (25, 40)
( ) (Sidirokastro Serres)
Decrease of plant-losses
12 12
() in new vineyard (Gefyra)
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Low quality zeolitic tuffs


, Zero crop-yield using low quality
zeolitic tuff from Petrota quarry
(40% ) (40% Clinoptilolite)
(: 2008, & 2009) (IGME: Gkertsis 2008, Marantos & Aggelatou 2009)
In Greenhouse-experiments
) ) Pepper - weight
) pH ) pH and electric conductivity of substrates
) C) Salad
) D) Chlorophyll measurements
) - - ) Humidity electric conductivity temperature in
hydroponic substrates
2 Field-experiments
) ) Sweet maize
) pH ) pH and electric conductivity

: Aquacultures: Cleaning the water and reducing


90% (3) ammonia by 90% by crossing three (3) sequential filters
( 1-8 mm). of HENAZE (grain size 1-8 mm).

: Air purification in fish feed plant: The strong malodor


reduction was achieved by passing the air through two (2)
(2) ( 20 cm) sequential filters (20 cm in thickness) of HENAZE (grain
( 8-25 mm). size 8-25 mm).

The addition of HENAZE in mortars of sand and Portland


Portland, 18%. cement, leads to a decrease of weight up to 18%. The increase of
, the HENAZE proportions, increases the porosity and water
, absorption of the lighter mortar and at the same time, decreases the
. uniaxial compressive strength.
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016, 2009, Vogiatzis et al. 2012)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

& - - - - -
Neutralization of sewage-sludge & production of odorless-cohesive zeo-sewage-sludge - - - Cultivation


- -
Starting
sewage-sludge Odorless and Odorless and
cohesive cohesive
zeo-sewage-sludge zeo-sewage-sludge

-
Fixation and prevent leaching of harmful substances from the zeo-sewage-sludge
- NO3- -
Seepage of NO3- and metals from Sewage-sludge and Zeo-sewage-sludge
Odorless and
--
cohesive
- -
zeo-sewage-sludge
Sewage Seepage water from Zeo-sewage- Seepage water from
-sludge Sewage-sludge Seepage sludge Zeo-sewage-sludge Seepage

(mg/kg) (mg/L) (%) (mg/kg) (mg/L) (%)

-
NO3- 19.92 19.92 100 65.08 12.40 19
Cr 0.08 0.02 25 0.10 Bdl 0
Odorless and Fe 0.18 0.04 22 0.22 0.02 9
cohesive Ni 0.20 0.02 10 0.22 Bdl 0
zeo-sewage-sludge Mn 0.28 0.02 7 0.30 Bdl 0
Bdl: / Below detection limit (<0,02)

The seepage of dangerous metals and components from the sewage-


7-100%, - 0-19%. sludge is 7-100%, while from the odorless and cohesive zeo-sewage-
, sludge 0-19%. The by decreasing the leaching of dangerous
, . components, protects the quality of soils, surface and ground waters.

T Considering the limit values of concentration for metals in sewage-


( 278/EEC/1986), - sludge (EU Directive 278/EEC/1986), the odorless and cohesive zeo-
, sewage-sludge is suitable for the reclamation of agricultural soils, but
. also for safe deposition.
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

& - - - - -
Neutralization of industrial-sludge & production of odorless-cohesive zeo-sludge - - - Safe deposition


- -

Starting Odorless and Odorless and


industrial cohesive cohesive
-sludge zeo-sludge zeo-sludge

-
Fixation and prevent leaching of harmful substances from the zeo-sludge
NO3- -
Seepage of NO3- and metals from dyeing-industry-sludge and zeo-sludge
- -
Odorless and cohesive zeo-sludge -
Dyeing- Seepage water from Dyeing- Zeo- Seepage water
industry-sludge industry-sludge Seepage sludge from Zeo-sludge Seepage
(mg/kg) (mg/L) (%) (mg/kg) (mg/L) (%)
NO3- 26.64 26.56 100 73.48 13.22 18
Cr 0.05 0.02 40 0.06 Bdl 0
- Bdl: / Below detection limit (<0,02)
Odorless and cohesive zeo-sludge

The seepage of dangerous metals and components from the


40-100%, - industrial-sludge is 40-100%, while from the odorless and cohesive
0-18%. -, zeo-sludge 0-18%. The odorless and cohesive zeo-sludge, is
, suitable for safe deposition, because of the fixation of harmful
/- - - , substances in the nano/micro- meso- and macropores of the
HENAZE, they are not leached and not transported by rainwater in
, , the aquatic environment, thus protecting the quality of soils,
. surface and ground waters.
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

Neutralization of dangerous industrial solid wastes


(.., ) - - - (e.g., batteries) - - - Safe deposition

Solid
wastes
of batteries

Neutralized
solid
wastes
of batteries
by HENAZE

The neutralized dangerous industrial solid wastes (such


( ), as solid waste of batteries), are suitable for safe
, deposition, because of the fixation of harmful
/- - substances in the nano/micro- meso- and macropores of
, the HENAZE, they are not leached and not transported
, by rainwater in the aquatic environment, thus
, protecting the quality of soils, surface and ground
. waters.
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

() Neutralization of mine solid wastes (mine-tailings)


- - - and acid drainage - - - Safe deposition





()

The HENAZE effectively


The HENAZE effectively neutralize the acid
neutralize the dangerous mine drainage
mine solid wastes in constructed wetlands
(mine-tailings)

Mining and return the land for agricultural use


() (a) Treatment of acid mine drainage and mining wastewaters using HENAZE,
, neutralizes and makes the waters suitable for disposal in a natural recipient or
(.., : 87% Ag, 82% Hg). for irrigation (e.g., sorption ability of HENAZE: 87% Ag, 82% Hg).
() (b) Mixing of HENAZE with the mine solid wastes and mainly the mine-
(), / tailings, neutralizes the solid wastes / tailings and prevents the leaching of
. metals by the rainwater.
() (c) Mixing of HENAZE with soils of the mine to return to agricultural use,
, pH , adjust the pH of the soils to neutral, bring greater fertility and better quality of
, the agricultural products, as compared with the land before the mining of the
. metals.

(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

(U)
, (C) - - ? & (ZSS) -.
Purification of urban wastewaters Purification of (U) urban wastewaters by HENAZE and coagulants in batch-type experiments,
produced (C) clear water - - irrigation? & (ZSS) odorless and cohesive Zeo-Sewage Sludge.
(%), ()
Initial concentration Improvement (%), average (range)
pH 8.2-8.9 11 (7-18)
/ Color 1180-1700 mg/L Pt-scale 93 (88-97)

210-445 mg/L 94 (87-98)
Suspended particles
COD:
410-1275 mg/L 94 (89-97)
Chemical Oxygen Demand
P2O5 9.24-58.44 mg/L 97 (91-99)
NH4 30.52-110.76 mg/L 98 (97-99)
NO3- 42.30-75.70 mg/L 90 (86-92)
Cr 0.12-0.29 mg/L 86 (83-90)

&
& +
Starting - - Difference
Comparison between Urban Clear water Clear water after between
waste- after treatment Impro- treatment with Impro- Coagulants &
coagulants & HENAZE water with coagulants vement coagulants + HENAZE vement HENAZE
/ Color mg/L Pt-scale 1700 45 97 % 45 97 % 0%

445 10 98 % 10 98 % 0%
Suspended particles, mg/L (SS)
P2O5, mg/L 58.44 0.34 99 % 0.64 99 % 0%
COD:
1275 165 87 % 135 89 % +2%
Chemical Oxygen Demand, mg/L O2
Mn, mg/L 0.32 0.04 88 % 0.02 94 % +6%
Ni, mg/L 0.24 0.04 83 % 0.02 92 % +9%
Fe, mg/L 0.28 0.10 64 % 0.06 79 % + 15 %
Cr, mg/L 0.12 0.04 67 % 0.02 83 % + 16 %
NO3-, mg/L 75.70 55.78 26 % 10.62 86 % + 60 %

, Compared to the addition of coagulants, the addition of HENAZE improves the


~50%. purification of wastewaters on average by ~ 50%. The values of the clear water quality
, , parameters, after successive treatments, can be within the required limits for disposition
, , . as downstream, irrigation, swimming and fish waters.

(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

+
Urban Wastewater Treatment Plants + HENAZE

, - +
Sewage reception Sewage reception Sewage-sludge treatment, Thickening-Dewatering + HENAZE Desinfenction by ultraviolet radiation

, +
Sand & fat collection Denitrification, Aeration + HENAZE Secondary settling tanks
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

/ Purification of dyeing industry wastewaters


(D)
, (C) - - ? & (ZS) -.
Purification of (D) dyeing industry wastewaters by HENAZE and coagulants in batch-type experiments,
produced (C) clear water - - irrigation? & (ZS) odorless and cohesive Zeo-Sludge.
(%), ()
Initial concentration Improvement (%), average (range)
pH 7.5-9.0 7 (5-9)
/ Color 885-1524 mg/L Pt-scale 97
/ Suspended particles 105-151 mg/L 92 (91-93)
COD:
415-510 mg/L 90 (74-95)
Chemical Oxygen Demand
P2O5 7.01-16.06 mg/L 98
NH4 19.50-20.59 mg/L 98
NO3- 78.36 mg/L 94
Cr 0.08 mg/L 75



+
&
&
Starting - Clear water after - Difference
Comparison between Dyeing Clear water treatment with between
Coagulants industry after treatment Impro- coagulants + Impro- Coagulants &
& HENAZE wastewater with coagulants vement HENAZE vement HENAZE
/ Color, mg/L Pt-scale 885 30 97 % 30 97 % 0%

110 10 91 % 10 91 % 0%
Suspended particles, mg/L(SS)
P2O5, mg/L 16.06 0.28 98 % 0.30 98 % 0%
COD mg/L O2 510 150 71 % 135 74 % +3%
Cr, mg/L 0.08 0.03 63 % 0.02 75 % + 12 %
NO3-, mg/L 78.36 51.72 34 % 4.88 94 % + 60 %

, Compared to the addition of coagulants, the addition of HENAZE


~50%. improves the purification of wastewaters on average by ~ 50%.
, The values of the clear water quality parameters, after successive
, treatments, can be within the required limits for disposition as
, , . downstream, irrigation, swimming and fish waters.
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


Purification of industrial area wastewaters
(IN)

, (C) - - ?
& (ZS) -.
Purification of (IN) Thessaloniki industrial area
wastewaters by HENAZE and coagulants in batch-type
experiments, produced (C) clear water - - irrigation?
& (ZS) odorless and cohesive Zeo-Sludge.


()
Initial Improvement
concentration average (range)
(%)
pH 7.7-7.8 5 (4-6)
/ Color 929 mg/L Pt-scale 93
COD
239-255 mg/L 74 (69-77)
Chemical Oxygen Demand
P2O5 9.1-9.3 mg/L 97
NO3- 35.0-35.4 mg/L 60 (54-70)
Cr 35-40 g/L 85 (77-88)
Pb 3.0 g/L 48 (33-50)
, The values of the clear water quality parameters,
, after successive treatments, can be within the required
, limits for disposition as downstream, irrigation,
, . swimming and fish waters.

(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


Purification of Tanning-work wastewaters
(T)

, (C) - - ?
& (ZS) -
Purification of (T) tanning-work wastewaters by
HENAZE and coagulants in batch-type experiments,
produced (C) clear water - -irrigation?
& (ZS) odorless and cohesive Zeo-Sludge


()
Improvement
Initial average (range)
concentration (%)
pH 8.8 18

11200 mg/L Pt-scale 98
Color
1955 mg/L
99
Suspended particles
P2O5 61.97 mg/L 99
, The values of the clear water quality parameters,
, after successive treatments, can be within the required
, limits for disposition as downstream, irrigation,
, . swimming and fish waters.
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

(NO3-)
Removal of nitrates (NO3-) from wastewaters by HENAZE
(NO3-) / Reduction of (NO3-)

+
Wastewaters
with coagulants with HENAZE + coagulants
()
- 54 70 %
Sindos industrial area (Thessaloniki)
( )
26 % 86 92 %
Urban (Kilkis city)

34 % 94 %
Dyeing industry (Thessaloniki)


Purification of toxic and radioactive wastewaters with HENAZE
/ Sorption and removal (%)
Initial concentration (mg/L) Cd Hg Ag Th U Cs
1000 37 70 84 - - -
500 56 82 87 - - 60
100 - - - 55 37 70
50 - - - 58 40 -
(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)

Low quality zeolitic tuffs


Zero crop-yield using Low quality zeolitic tuff
(40% ) from Petrota quarry (40% Clinoptilolite)
(: 2008, & 2009) (IGME: Gkertsis 2008, Marantos & Aggelatou 2009)

* (Zn, Ni, Cr, Cu) *Removal of metals (Zn, Ni, Cr, Cu)
from wastewaters
* Fe Mn *Removal of Fe and Mn from potable water
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


Doirani Lake water Culture
&
/ before Sorption & removal of cyanobacteria by HENAZE / before
-




- Sorption-
Removal
Cyano- Initial after HENAZE

bacteria concentration treatment

Colonial 320
after HENAZE treatment 51 % after HENAZE treatment
Microcystis (colonies/mL)
Doirani 8254
Filamentous 75 %
Lake water (filaments/mL)
1433751
91 %
(cells/mL)
Chroococcus
Culture 478066
92 %
(cells/mL)

(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

() / Lake Koronia (Thessaloniki)



-
Polluted waters
Lakeside
zone-sludge

+ Lakes and surface waters + HENAZE


(1) , (1) The treatment of urban, industrial and agricultural wastewaters
, around the lake with HENAZE, improves the quality of waters
. before they flow into the lake.
(2) (2) The addition of HENAZE in the agricultural soils that are
, cultivated around the lake, prevents the seepage of dangerous
, substances by the rain water into the lake, increases the crops yield
. of agricultural products and improves their quality.
(3) , (3) The treatment of sewage-sludge, sludge and manure of industrial
and farm units with HENAZE around the lake, reduces the malodor
, and prevents the seepage of dangerous substances by the rain water
. into the lake.
(4) , (4) The addition of HENAZE in the lakeside sludge, reduces the
, malodor, improves the living and growth conditions for organisms
. and plants in the lakeside zone.
(5) , pH (5) The addition of HENAZE into the lake-water, controls to neutral
, , the pH of water, enriches with oxygen the water, reduces the
, bacteria, improves the living and growth conditions for organisms
. , and plants of the lake. Some biologists suggest, before throwing the
, HENAZE into the natural aquatic ecosystems, it should be explored
() the impacts on water due to a possible decrease of (a) beneficial
, () () phytoplankton, (b) microbial diversity and (c) microorganisms that
determine the quality of water as heterotrophic bacteria and
. protozoa.

(e.g., 2002-2016, & 2002, .. 2006-2016, Filippidis et al. 2007-2016, Filippidis 2007-2016)
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

: Purification of industrial wastewaters:


(), Cheese-dairy, Olive-press,
( ), , , Lubricates-oils, Pickles, etc

/ after
/ before
/ before / after

/ Cheese-dairy / Olive-press

/ before
/ after

/ Lubricates-oils T / Pickles
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

, - Challenging insects, spraying fruit-


bearing trees by adding HENAZE in
the insecticide-solution

Olive-trees

Monaco Mitteregger 2013


. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

, Some Agricultural, Industrial and


Environmental Applications
* *Soil amendment for agriculture
* pH *Conditioning of acid and alkaline soils
* *Greenhouse substrates, Substrates for flowers
* *Stronger and healthier grass.
* *Treating agricultural waste and converting manure into odorless fertilizer
* - *Neutralization of sewage-sludge and production of odorless-cohesive
- , zeo-sewage-sludge for agricultural use, as well as for safe deposition
* , *Sanitation of soils in mines and quarries
*- (- , .) *Neutralization-sanitation of polluted soils (heavy-toxic metals, etc.)
* *Mine waste management and land return to agricultural use
* , , *Hygiene and food safety, improvement of taste, quality and
preservation of food
*: . *Aquaculture: Water Purification. Reduction of ammonia in water
* ( ) *Purification of municipal sewage (Sewage Treatment Plants)
* (, , , *Purification of industrial wastewater (dyeing, tanneries,
, , -, - lubricates-oils, industrial zones, pickles, cheese-dairy,
, ) olive-press, etc.)
* - *Neutralization of industrial-sludge and production of odorless-cohesive
- zeo-sludge for safe deposition
* *Neutralization of dangerous industrial solid wastes
* () *Improvement and oxygen enrichment of surface waters (Lakes)
and aqua ecosystems
* *Sorption and removal of cyanobacteria
* *Sorption and removal of heavy metals
and toxic concentrations of metals
* . *Sorption and removal of radionuclides.
. Purification of radioactive wastewaters
* *Improvement of constructed wetlands and water treatment units
* , *Improvement of the drinking water quality,
water in swimming pools and aquariums
* , *Deodorant material, sand hygiene for pets
* *Air purification and malodor reduction
* *Purification and drying of gases

5 >170 5 patents and >170 publications in my website


http://anestis.webpages.auth.gr http://anestis.webpages.auth.gr
- , Attention Strict Quality Control of Mineralogical, morpho-
, , logical, chemical and radiological composition, THANK YOU
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr


[1] / Text Books and Monographs
[1.11] ., . , , ,
121., 2002.
[1.13] ., ., ()
. , , , 28., 2011.
[1.14] ., ., . , , ,
34., 2011.
[1.15] ., ., . , ,
, 53., 2012.
[1.17] ., . , , , 14 ., 2012.
[1.18] ., ., : . , ,
, 46., 2013.
[1.19] Filippidis A., Environmental, agricultural, aquacultural and industrial uses of high quality HEU-type (clinoptilolite-heulandite) natural zeolite. School of
Geology, Faculty of Sciences, Aristotle University of Thessaloniki, Greece, 13p., 2013.
[1.20] ., 1982-2014. ,
, , 20., 2014.
[1.22] ., () 1982-2015.
, , , 24., 2015.

[2] / Patents
[2.01] ., ., ., ., ., .,
. . 1006140, , , 05.11.2008.
[2.02] ., ., ., ., ., ., .
. 1006145, , , 07.11.2008.
[2.03] ., ., ., ., ., .,
. . 1006146, , , 10.11.2008.
[2.04] ., ., ., ., . . 1007414,
, , 27.09.2011.
[2.05] ., ., ,
, . . 1007446, , , 26.10.2011.

[3] / International Journals


[3.08] Filippidis A., Kougoulis C., Michailidis K., Sr-bearing stilbite in a quartz-monzonite from Vathi, Kilkis, Northern Greece. Schweizerische Mineralogische und
Petrographische Mitteilungen, 68, 67-76, 1988.
[3.09] Morad S., Filippidis A., AlDahan A.A., Collini B., Ounchanum P., Stellerite and Sr-containing stilbite in granitic rocks from the Siljan ring structure, central
Sweden. Bulletin of the Geological Institutions of the University of Uppsala, 12, 143-149, 1989.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr
[3.14] Kirov G.N., Filippidis A., Tsirambidis A., Tzvetanov R.G., Kassoli-Fournaraki A., Zeolite-bearing rocks in Petrota area (Eastern Rhodope Massif, Greece).
Geologica Rhodopica, 2, 500-511, 1990.
[3.22] Tsirambides A., Filippidis A., Kassoli-Fournaraki A., Zeolitic alteration of Eocene volcaniclastic sediments at Metaxades, Thrace, Greece. Applied Clay
Science, 7, 509-526, 1993.
[3.23] Filippidis A., New find of moissanite in the Metaxades zeolite-bearing volcaniclastic rocks, Thrace county, Greece. Neues Jahrbuch fur Mineralogie
Monatshefte, 11, 521-527, 1993.
[3.24] Misaelides P., Godelitsas A., Haristos D., Noli F., Filippidis A., Sikalidis C., Determination of heavy metal uptake by the sodium form of heulandite using
radiochemical techniques. Geologica Carpathica-Series Clays, 44(2), 115-119, 1993.
[3.26] Misaelides P., Godelitsas A., Filippidis A., Charistos D., Anousis I., Thorium and uranium uptake by natural zeolitic materials. The Science of the Total
Environment, 173/174, 237-246, 1995.
[3.28] Misaelides P., Godelitsas A., Filippidis A., The use of zeoliferous rocks from Metaxades-Thrace, Greece, for the removal of caesium from aqueous solutions.
Fresenius Environmental Bulletin, 4, 227-231, 1995.
[3.29] Koutles Th., Kassoli-Fournaraki A., Filippidis A., Tsirambides A., Geology and geochemistry of the Eocene zeolitic-bearing volcaniclastic sediments of
Metaxades, Thrace, Greece. Estudios Geologicos, 51(1-2), 19-27, 1995.
[3.33] Filippidis A., Godelitsas A., Charistos D., Misaelides P., Kassoli-Fournaraki A., The chemical behavior of natural zeolites in aqueous environments:
Interactions between low-silica zeolites and 1M NaCl solutions of different initial pH-values. Applied Clay Science, 11, 199-209, 1996.
[3.34] Godelitsas A., Misaelides P., Charistos D., Filippidis A., Anousis I., Interaction of HEU-type zeolite crystals with Thorium aqueous solutions. Chemie der Erde
- Geochemistry, 56, 143-156, 1996.
[3.35] Godelitsas A., Misaelides P., Filippidis A., Charistos D., Anousis I., Uranium sorption from aqueous solutions on sodium-form of HEU-type zeolite crystals.
Journal of Radioanalytical and Nuclear Chemistry, Articles, 208(2), 393-402, 1996.
[3.37] Filippidis A., Godelitsas A., Charistos D., Tsipis C., Natrolite/thomsonite intergrowths from basaltic rocks of Deccan Traps (Western India). Neues Jahrbuch
fur Mineralogie Monatshefte, 4, 161-170, 1996.
[3.38] Charistos D., Godelitsas A., Tsipis C., Sofoniou M., Dwyer J., Manos G., Filippidis A., Triantafyllidis C., Interaction of natrolite and thomsonite intergrowths
with aqueous solutions of different initial pH values at 25o C in the presence of KCl: Reaction mechanisms. Applied Geochemistry, 12, 693-703, 1997.
[3.40] Tserveni-Gousi A.S., Yannakopoulos A.L., Katsaounis N.K., Filippidis A., Kassoli-Fournaraki A., Some interior egg characteristics as influenced by addition
of Greek clinoptilolitic rock material in the hen diet. Archiv fur Geflugelkunde, 61(6), 291-296, 1997.
[3.45] Godelitsas A., Charistos D., Dwyer J., Tsipis C., Filippidis A., Hatzidimitriou A., Pavlidou E., Copper (II)-loaded HEU-type zeolite crystals: characterization
and evidence of surface complexation with N,N-diethyldithiocarbamate anions. Microporous and Mesoporous Materials, 33, 77-87, 1999.
[3.48] Godelitsas A., Charistos D., Tsipis A., Tsipis C., Filippidis A., Triantafyllidis C., Manos G., Siapkas D., Characterisation of zeolitic materials with a HEU-type
structure modified by transition metal elements: Definition of acid sites in Nickel-loaded crystals in the light of experimental and quantum-chemical results.
Chemistry European Journal, 7(17), 3705-3721, 2001.
[3.49] Barbieri M., Castorina F., Masi U., Garbarino C., Nicoletti M., Kassoli-Fournaraki A., Filippidis A., Mignardi S., Geochemical and isotopic evidence for the
origin of rhyolites from Petrota (Northern Thrace, Greece) and geodynamic significance. Chemie der Erde - Geochemistry, 61, 13-29, 2001.
[3.58] Mouhtaris Th., Charistos D., Kantiranis N., Filippidis A., Kassoli-Fournaraki A., Tsirambidis A., GIS-type zeolite synthesis from Greek lignite sulphocalcic fly
ashes promoted by NaOH solutions. Microporous and Mesoporous Materials, 61, 57-67, 2003.
[3.59] Godelitsas A., Charistos D., Tsipis C., Misaelides P., Filippidis A., Schindler M., Heterostructures patterned on aluminosilicate microporous substrates:
Crystallisation of cobalt (III) tris(N,N-diethyldithiocarbamato) on the surface of HEU-type zeolite. Microporous and Mesoporous Materials, 61, 69-77, 2003.
[3.64] Kantiranis N., Filippidis A., Mouhtaris T., Paraskevopoulos K.M., Zorba T., Squires C., Charistos D., EPI-type zeolite synthesis from Greek sulphocalcic fly
ashes promoted by H2O2 solutions. Fuel, 85, 360-366, 2006.
[3.65] Kantiranis N., Chrissafis C., Filippidis A., Paraskevopoulos K., Thermal distinction of HEU-type mineral phases contained in Greek zeolite-rich volcaniclastic
tuffs. European Journal of Mineralogy, 18(4), 509-516, 2006.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr
[3.66] Filippidis A., Kantiranis N., Experimental neutralization of lake and stream waters from N. Greece using domestic HEU-type rich natural zeolitic material. Desalination, 213, 47-55,
2007.
[3.68] Filippidis A., Apostolidis N., Paragios I., Filippidis S., Zeolites clean up. Industrial Minerals, 487(April), 68-71, 2008.
[3.71] Petrotou A., Skordas K., Papastergios G., Filippidis A., Concentrations and bioavailability of potentially toxic elements in soils of an industrialised area of Northwestern Greece.
Fresenius Environmental Bulletin, 19(12), 2769-2776, 2010.
[3.75] Kantiranis N., Sikalidis K., Godelitsas A., Squires C., Papastergios G., Filippidis A., Extra-framework cation release from heulandite-type rich tuffs on exchange with NH4+. Journal
of Environmental Management, 92, 1569-1576, 2011.
[3.76] Tzamos E., Kantiranis N., Papastergios G., Vogiatzis D., Filippidis A., Sikalidis C., Ammonium exchange capacity of the Xerovouni zeolitic tuffs, Avdella area, Evros Prefecture,
Greece. Clay Minerals, 46, 179-187, 2011.
[3.77] Petrotou A., Skordas K., Papastergios G., Filippidis A., Factors affecting the distribution of potentially toxic elements in surface soils around an industrialized area of northwestern
Greece. Environmental Earth Sciences, 65(3), 823-833, 2012.
[3.78] Tsirambides A., Filippidis A., Greece seeks mineral lifeboat. Industrial Minerals, 532(January), 38-45, 2012.
[3.79] Tsirambides A., Filippidis A., Exploration key to growing Greek industry. Industrial Minerals, 533(February), 44-47, 2012.
[3.81] Tsirambides A., Filippidis A., Energy mineral resources of Greece. Journal of Environmental Science and Engineering, B1, 709-719, 2012.
[3.84] Vogiatzis D., Kantiranis N., Filippidis A., Tzamos E., Sikalidis C., Hellenic Natural Zeolite as a replacement of sand in mortar: Mineralogy monitoring and evaluation of its influence
on mechanical properties. Geosciences, 2, 298-307, 2012.
[3.85] Tsirambides A., Filippidis A., Metallic mineral resources of Greece. Central European Journal of Geosciences, 4(4), 641-650, 2012.
[3.86] Filippidis A., Industrial and municipal wastewater treatment by zeolitic tuff. Water Today, January, Volume-V (issue-X), 34-38, 2013.
[3.88] Skordas K., Papastergios G., Filippidis A., Major and trace element contents in apples from a cultivated area of central Greece. Environmental Monitoring and Assessment, 185,
8465-8471, 2013.
[3.92] Filippidis A., Kantiranis N., Papastergios G., Filippidis S., Safe management of municipal wastewater and sludge by fixation of pollutants in very high quality HEU-type zeolitic tuff.
Journal of Basic and Applied Research International, 7(1), 1-8, 2015.
[3.94] Filippidis A., Papastergios G., Kantiranis N., Filippidis S., Neutralization of dyeing industry wastewater and sludge by fixation of pollutants in very high quality HEU-type zeolitic
tuff. Journal of Global Ecology and Environment, 2(4), 221-226, 2015.
[3.99] Filippidis A., Tziritis E., Kantiranis N., Tzamos E., Gamaletsos P., Papastergios G., Filippidis S., Application of Hellenic Natural Zeolite in Thessaloniki industrial area wastewater
treatment. Desalination and Water Treatment, doi: 10.1080/19443994.2015, 2016.
[3.101] Papastergios G., Kantiranis N., Filippidis A., Sikalidis C., Vogiatzis D., Tzamos E., HEU-type zeolitic tuff in fixed bed columns as decontaminating agent for liquid phases.
Desalination and Water Treatment, 59, 94-98, 2017.
[4] / Hellenic Journals
[4.2] Tsirambides A., Kassoli-Fournaraki A., Filippidis A., Soldatos K., Preliminary results on clinoptilolite-containing volcaniclastic sediments from Metaxades, NE Greece. Bulletin of the
Geological Society of Greece, 23(2), 451-460, 1989.
[4.6] Godelitsas A., Charistos D., Zorba T., Filippidis A., Siapkas D., FT-IR spectroscopic study of fibrous natural zeolites. Bulletin of the Geological Society of Greece, 30(3), 301-309,
1994.
[4.7] ., ., - ., ., - NaOH 0,5.
, 33, 69-74, 1999.
[4.12] Kantiranis N., Stamatakis M., Filippidis A., Squires C., The uptake ability of the clinoptilolitic tuffs of Samos Island, Greece. Bulletin of the Geological Society of Greece, 36(1), 89-
96, 2004.
[4.18] ., ., , , .
, 37, 90-101, 2005.
[4.19] Filippidis A., Kantiranis N., Stamatakis M., Drakoulis A., Tzamos E., The cation exchange capacity of the Greek zeolitic rocks. Bulletin of the Geological Society of Greece, 40(2),
723-735, 2007.
[4.21] Kantiranis N., Filippidis A., Vouta S., Drakoulis A., Koutles Th., Tzamos E., The cation exchange capacity of industrial minerals and rocks of Milos Island. Bulletin of the
Geological Society of Greece, 40(2), 775-780, 2007.
[4.25] Filippidis A., Papastergios G., Apostolidis N., Filippidis S., Paragios I., Sikalidis C., Purification of urban wastewaters by Hellenic Natural Zeolite. Bulletin of the Geological Society
of Greece, 43(5), 2597-2605, 2010.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

[4.26] Tzamos E., Filippidis A., Kantiranis N., Sikalidis C., Tsirambidis A., Papastergios G., Vogiatzis D., Uptake ability of zeolitic rock from South Xerovouni,
Avdella, Evros, Hellas. Bulletin of the Geological Society of Greece, 43(5), 2762-2772, 2010.
[4.27] Filippidis A., Environmental, industrial and agricultural applications of Hellenic Natural Zeolite. Hellenic Journal of Geosciences, 45, 91-100, 2010.
[4.28] Filippidis A., Purification of municipal wastewaters and production of odorless and cohesive zeo-sewage sludge, using Hellenic Natural Zeolite. Scientific
Annals, School of Geology, Aristotle University of Thessaloniki, 100, 55-62, 2010.
[4.29] Kantiranis N., Sikalidis C., Papastergios G., Squires C., Filippidis A., Continuous extra-framework Na+ release from Greek Analcime-rich volcaniclastic rocks
on exchange with NH4+. Scientific Annals, School of Geology, Aristotle University of Thessaloniki, 100, 81-87, 2010.
[4.32] ., ., ., ., ., ., ., ., ,
- (, ). , ,
, 101, 119-124, 2012.
[4.33] ., ., , , ,
: . , , , 101, 125-133, 2012.
[4.35] Filippidis A., Godelitsas A., Kantiranis N., Gamaletsos P., Tzamos E., Filippidis S., Neutralization of sludge and purification of wastewater from Sindos
industrial area of Thessaloniki (Greece) using natural zeolite. Bulletin of the Geological Society of Greece, 47(2), 920-926, 2013.
[4.39] ., ., ., ., , ,
. , , , 103, 51-54, 2015.
[4.40] ., -HEU. ,
, , 103, 73-76, 2015.
[4.41] ., - . ,
, , 103, 77-80, 2015.
[4.42] ., (NO3-) (). ,
, , 105, 81-87, 2016.
[4.43] ., ., . , ,
, 105, 89-95, 2016.
[4.45] Filippidis A., Applications of the Hellenic Natural Zeolite (HENAZE) and specifications of zeolitic tuffs. Bulletin of the Geological Society of Greece, 50 (4),
1809-1819, 2016.
[4.46] Filippidis A., Kantiranis N., Tsirambides A., The mineralogical composition of Thrace zeolitic rocks and their potential use as feed additives and nutrition
supplements. Bulletin of the Geological Society of Greece, 50 (4), 1820-1828, 2016.
[4.49] Hatzigiannakis E., Kantiranis N., Tziritis E., Filippidis A., Arampatzis G., Tzamos E., The use of HEU-type zeolitic tuff in sustainable agriculture:
Experimental study on the decrease of nitrate load in vadose zone leachates. Bulletin of the Geological Society of Greece, 50 (4), 2143-2154, 2016.

[5] / International Congress Proceedings and Special Volumes


[5.13] Kassoli-Fournaraki A., Stamatakis M., Hall A., Filippidis A., Michailidis K., Tsirambides A., Koutles Th., The Ca-rich clinoptilolite deposit of Pentalofos,
Thrace, Greece. In: Natural Zeolites for the Third Millennium (C. Colella & F.A. Mumpton, eds), De Frede Editore, Napoli, 193-202, 2000.
[5.14] Yannakopoulos A., Tserveni-Gousi A., Kassoli-Fournaraki A., Tsirambides A., Michailidis K., Filippidis A., Lutat U., Effects of dietary clinoptilolite-rich tuff
on the performance of growing-finishing pigs. In: Natural Zeolites for the Third Millennium (C. Colella & F.A. Mumpton, eds), De Frede Editore, Napoli, 471-481,
2000.
[5.15] Filippidis A., Kassoli-Fournaraki A., Environmental uses of natural zeolites from Evros district, Thrace, Greece. Fifth International Conference on
Environmental Pollution, Thessaloniki, Greece, 28/08-1/09/2000, Proceedings, 149-155, 2000.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

[5.21] Filippidis A., Apostolidis N., Filippidis S., Paragios I., Purification of industrial and urban wastewaters, production of odorless and cohesive zeo-sewage sludge
using Hellenic Natural Zeolite. Second International Conference on Small and Decentralized Water and Wastewater Treatment Plants, Skiathos, Greece, 2-4/05/2008,
Proceedings, 403-408, 2008.
[5.22] Filippidis A., Apostolidis N., Paragios I., Filippidis S., Purification of dye-work and urban wastewaters, production of odorless and cohesive zeo-sewage
sludge, using Hellenic Natural Zeolite. 1st International Conference on Hazardous Waste Management, Chania, Crete, Greece, 1-3/10/2008, Proceedings, 8p., 2008.
[5.23] Filippidis A., Apostolidis N., Paragios I., Filippidis S., Safe management of sewage sludge, produced by treatment of municipal sewage with Hellenic Natural
Zeolite. AQUA, 3rd International Conference on Water Science and Technology with emphasis on water and climate, Athens, Greece, 16-19/10/2008, Proceedings,
5p., 2008.
[5.24] Filippidis A., Treatment and recycling of municipal and industrial waste waters using Hellenic Natural Zeolite: A Review. AQUA, 3rd International Conference
on Water Science and Technology with emphasis on water and climate, Athens, Greece, 16-19/10/2008, Proceedings, 5p., 2008.
[5.25] Filippidis A., Papastergios G., Apostolidis N., Paragios I., Filippidis S., Sikalidis C., Oderless and cohesive zeo-sewage sludge produced by Hellenic Natural
Zeolite treatment. 3rd AMIREG International Conference on Assessing the Footprint of Resource Utilization and Hazardous Waste Management, Athens, Greece, 7-
9/09/2009, Proceedings, 96-100, 2009.
[5.27] Filippidis A., Moustaka-Gouni M., Papastergios G., Katsiapi M., Kantiranis N., Karamitsou V., Vogiatzis D., Filippidis S., Cyanobacteria removal by Hellenic
Natural Zeolite. Third International Conference on Small and Decentralized Water and Wastewater Treatment Plants, Skiathos, Greece, 14-16/05/2010, Proceedings,
383-387, 2010.
[5.29] Filippidis A., Tsirambides A., Kantiranis N., Tzamos E., Vogiatzis D., Papastergios G., Papadopoulos A., Filippidis S., Purification of wastewater from Sindos
industrial area of Thessaloniki (N. Greece) using Hellenic Natural Zeolite. 9th International Hydrogeological Congress, Kalavrita, Greece, 5-8/10/2011. Environmental
Earth Sciences, Springer-Verlag Berlin, Advances in the Research of Aquatic Environment (N. Lambrakis, G. Stournaras, K. Katsanou, eds), Volume 2, 435-442,
2011.
[5.30] Filippidis A., Kantiranis N., Vogiatzis D., Tzamos E., Papastergios G., Filippidis S., Odourless-cohesive zeosewage sludge production and urban wastewater
purification by natural zeolite. International Conference Protection and Restoration of the Environment XI, Thessaloniki, Greece, 3-6/07/2012, Proceedings, 582-588,
2012.
[5.34] Filippidis A., Kantiranis N., Tziritis E., Tzamos E., Vogiatzis D., Filippidis S., The use of Hellenic Natural Zeolite (HENAZE) in the purification of
Thessaloniki industrial area wastewaters. 10th International Hydrogeological Congress of Greece, Thessaloniki, Greece, 8-10/10/2014, Proceedings, 187-193, 2014.

[6] / Hellenic Congress Proceedings and Special Volumes


[6.1] ., ., ., (. , ). 15
, , 6-10/12/1994, , , 218-221, 1994.
[6.2] ., ., ., ., .., ., ., HEU XRD , 29Si
& 27Al MAS NMR, FT-IR XPS-ESCA. 15 , , 6-10/12/1994, , , 485-488, 1994.
[6.4] ., - ., ., .,
pH. 4 , , 14-16/11/1997, , 539-546, 1997.
[6.11] ., ., - ., .,
. 1 , , , 12-
13/02/2000, , 308-318, 2000.
[6.15] ., - .,
-. 1 , , , 12-
13/02/2000, , 506-515, 2000.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

[6.17] ., . , , 24-
26/09/1999, , 449-459, 2001.
[6.20] ., - ., . 12
, , 2-5/12/2002, , 75-82, 2002.
[6.21] Filippidis A., Kantiranis N., Drakoulis A., Vogiatzis D., Quality, pollution, treatment and management of drinking, waste, underground and surface waters, using
analcime-rich zeolitic tuff from Samos island, Hellas. 7th Hellenic Hydrogeological Conference, Athens, Greece, 4-6/10/2005, Proceedings, Volume II, 219-224, 2005.
[6.25] ., . 13 ,
, 28/11-1/12/2005, , 73-84, 2005.
[6.26] ., ., ., ., . 2
, , 1-4/06/2006, , 273-279, 2006.
[6.27] ., , , .
, , 4/08/2007, , 89-107, 2007.
[6.28] ., ., ., .,
. Jean Monnet: , , 30/11-1/12/2007, , 557-569, 2007.
[6.29] ., ., ., ., , ,
. 3 , , 14-17/03/2008, , 8., 2008.
[6.30] ., ., ., - ., ., ., .,
-- . 1 , , 21-23/05/2008, ,
, 1099-1110, 2008.
[6.31] ., ., ., ., -
. 8 , , 7-10/10/2008, , 2, 783-788, 2008.
[6.32] ., ., ., ., , -
. 8 , , 7-10/10/2008, , 2, 789-798, 2008.
[6.33] ., . . ,
, , 27-30/05/2009, , , 829-836, 2009.
[6.34] ., ., ., ., -
. , , , , 425-434, 2009.
[6.37] ., - ., ., ., . 4
, , 18-20/03/2011, , 9., 2011.
[6.38] ., ., ., ., ., ., ., .,
( ) . 4 , , 18-
20/03/2011, , 8., 2011.
[6.41] ., ., ., ., ., ., ., .,
. 21 , , 9-12/12/2011, , 8., 2011.
[6.42] ., ., ., ., ., - - - .
4 , , 30/11-1/12/2012, , 355-360, 2012.
[6.44] ., ., : ,
. .
- 2007-2013, , , 5/05/2015, , 12., 2015.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

[7] / Extended Abstracts


[7.3] Savin S.M., Tsirambides A., Kassoli-Fournaraki A., Filippidis A., Oxygen-isotope evidence for the alteration of the Eocene zeolite-bearing volcaniclastic
sediments of Metaxades, Thrace, Greece. 4th International Conference on the Occurrence, Properties and Utilization of Natural Zeolites, Boise, Idaho, USA, 20-
28/06/1993, Extended Abstracts, 180-181, 1993.
[7.7] Tserveni-Gousi A.S., Yannakopoulos A.L., Katsaounis N.K., Filippidis A., Kassoli-Fournaraki A., Fortomaris P., The influence of Greek clinoptilolite-bearing
rocks on the egg shell quality, in the early stage of laying. International Symposium and Exhibition on Natural Zeolites, Sofia, Bulgaria, 18-25/06/1995, Extended
Abstracts, 118, 1995.
[7.8] Yannakopoulos A.L., Tserveni-Gousi A.S., Katsaounis N.K., Kassoli-Fournaraki A., Filippidis A., Tsolakidou A., The influence of Greek clinoptilolite-bearing
rocks on the performance of laying hens, in the early stage of laying. International Symposium and Exhibition on Natural Zeolites, Sofia, Bulgaria, 18-25/06/1995,
Extended Abstracts, 120, 1995.
[7.9] .., - .., .., - ., .,
. 11 , , 2-
3/11/1995. , 17, 43-44, 1996.
[7.12] Yannakopoulos A., Tserveni-Gousi A., Kassoli-Fournaraki A., Lutat U., Michailidis K., Filippidis A., Tsirambides A., Some results in swines performance
after adding natural Greek zeolite in their diets. 5th International Conference on the Occurrence, Properties and Utilization of Natural Zeolites, Ischia, Naples, Italy,
21-29/09/1997, Extended Abstracts, 329-332, 1997.
[7.16] Yannakopoulos A., Tserveni-Gousi A., Fortomaris P., Arsenos G., Filippidis A., Kassoli-Fournaraki A., Effects of dietary inclusion of natural Greek zeolite on
the reproductive characteristics of sows. 6th International Conference on Occurrence, Properties and Utilization of Natural Zeolites, Thessaloniki, Greece, 3-
7/06/2002, Extended Abstracts, 393-394, 2002.
[7.19] ., ., ., .,
. 3 , , 1-2/11/2007, , 110-112, 2007.
[7.22] Filippidis A., Moustaka-Gouni M., Kantiranis N., Katsiapi M., Papastergios G., Karamitsou V., Vogiatzis D., Filippidis S., Chroococcus (cyanobacteria)
removal by hellenic natural zeolite. 8th International Conference on the Occurrence, Properties and Utilization of Natural Zeolites, Sofia, Bulgaria, 10-18/07/2010,
Extended Abstracts, 91-92, 2010.

[8] / Abstracts
[8.9] Tsirambides A., Kassoli-Fournaraki A., Filippidis A., Soldatos K., Preliminary results on clinoptilolite-containing volcaniclastic sediments from Metaxades, NE
Greece. 4th Congress of the Geological Society of Greece, Athens, Greece, 25-27/05/1988, Abstracts, p.110-111, 1988.
[8.11] Kirov G.N., Filippidis A., Tsirambidis A., Tzvetanov R.G., Kassoli-Fournaraki A., Zeolite-bearing rocks in Petrota area (Eastern Rhodope Massif, Greece). 2nd
Hellenic-Bulgarian Symposium for the Rhodope Massif, Thessaloniki, Greece, 14-17/10/1989, Abstracts, p.100, 1989.
[8.19] ., ., ., ., - ., .,
. :
, , 20/02/1995, , .7, 1995.
[8.29] ., ,
. , , 23/11/2008, , 1., 2008.
[8.39] Filippousi M., Pavlidou E., Zamboulis D., Filippidis A., Papadopoulou L., Katsikini M., Paloura E., Tzamos E., Van Tendeloo G., Sorption of zinc and silver
by nanozeolitic tuff. 9 th International Conference on Nanosciences and Nanotechnologies, Thessaloniki, Greece, 3-6/07/2012, Abstracts, p.259, 2012.
. , -, ,
A. Filippidis, Professor of Mineralogy-Economic Geology, Head of the Lab.of Geochemistry, Aristotle University of Thessaloniki, Website: http://anestis.webpages.auth.gr

[9] / Research Reports


[9.7] Kassoli-Fournaraki A., Filippidis A., Tsirambides A., Michailidis K., Yannakopoulos A., Tserveni-Gousi A., Development of industrial and environmental
uses of European natural zeolites. Research Report, Thessaloniki, Greece, 115p., 1998.
[9.13] ., ., Squires C., .
, , 25., 2005.

[10] / Field Guides and Articles


[10.1] Filippidis A., Kassoli-Fournaraki A., Tsirambides A., The zeolites of Petrota and Metaxades (Thrace) and the kaolins of Leucogia (Macedonia), Greece.
International Symposium and Exhibition on Natural Zeolites, Sofia, Bulgaria, 18-25/06/1995, Field Trip Guide (B. Aleksiev, ed.), 49-62, 1995.
[10.3] ., , , .
, 7, 14-16, 2010.
[10.4] ., ., . , 126, 22-26, 2012.
[10.5] ., : , . , ., , 8., 2013.
[10.6] ., : () .
, 2 (), .7., 2013.

[11] / Feasibility Studies


[11.8] ., ., : , , , -
. & , , 5p., 2002.
[11.14] ., : . &
, , 10., 2005.
[11.25] Filippidis A., Mineralogical Study of Natural Zeolites on behalf of GEO-VET. Thessaloniki, Greece, 2p., 2012.
[11.35] ., () ZEOVET. , 3., 2015.

21 / Extended abstracts
16 / Abstracts
4 / Research Reports
6 / Field guides and articles
7 / Feasibility studies