UNIVERSITY OF NOVA GORICA GRADUATE SCHOOL · EVALUATION OF MARINE SEDIMENTS FROM THE PORT OF LUKA...

UNIVERSITY OF NOVA GORICA

GRADUATE SCHOOL

EVALUATION OF MARINE SEDIMENTS FROM THE

PORT OF LUKA KOPER FROM THE

ENVIRONMENTAL PERSPECTIVE AND IN TERMS OF

THEIR USABILITY IN THE BRICK INDUSTRY

MASTER'S THESIS

Patrik Baksa

Mentors: Dr. Vilma Ducman

Assist. Prof. Rebeka Kovačič Lukman

Nova Gorica, 2016

UNIVERZA V NOVI GORICI

FAKULTETA ZA PODIPLOMSKI ŠTUDIJ

OVREDNOTENJE MORSKIH SEDIMENTOV IZ

PRISTANIŠČA LUKE KOPER IZ OKOLJSKEGA

VIDIKA IN VIDIKA UPORABNOSTI V OPEKARSKI

INDUSTRIJI

MAGISTRSKA NALOGA

Patrik Baksa

Mentorici: dr.Vilma Ducman

doc. dr. Rebeka Kovačič Lukman

Nova Gorica, 2016

“Beliefs are just thoughts that you keep thinking.

Change your mind and your life will follow.”

ACKNOWLEDGEMENTS

I would like to express my sincere gratitude and appreciation to my mentors, Assist.

Prof. Rebeka Kovačič Lukman and Dr. Vilma Ducman, for their professional

guidance and support in carrying out this research work. Their useful suggestions and

constructive criticism have helped me to successfully complete my Master’s thesis.

I also wish to thank all my friends for their support. Special thanks to Borut Poljšak,

Janja Sterle, and Amela Fatkič, who helped me with my studies; to my best friends

Erik Vigini, Robi Krstić, Matjaž Jerman, Daniel Babelić, Lora Pemper, Miro Badrić,

the Penko and Ramis families; and to my coworkers Franka Cepak, Matej Cah,

Bojan Kovačič and Matej Fabjan.

Very special thanks go to my family, my mother Emilija, my father Ivan (who

unfortunately did not live long enough to see me completing my studies), my brother

Dean, his wife Lara and Tilen, for all their help, understanding, love, and support.

This Master's thesis will not save the world, but it will save me in the long run –

because it will always remind that I can complete anything I have started, no matter

the obstacles. Everything can be done and I will always keep walking. If you lose

strength along the way, take the time to relax and find your motivation again.

I

ABSTRACT

The majority of the world’s goods are transported over water and dredging is

essential for the development of harbors and ports. Therefore, the management of

dredged material is a worldwide issue. Due to its chemical and petrographic,

mineralogical and homogeneity composition, marine sediments are an appropriate

raw material to use in the brick industry. Marine sediments can serve as raw material

for the production of clay blocks, roofing and ceramic tiles.

Different analyses were carried out in order to determine if the dredged material from

the Port of Koper is environmentally friendly and suitable to use in the brick

industry. These analyses included: a chemical analysis, a mineralogical analysis, a

particle size analysis and a chloride content (Cl-) analysis, and tests of firing in a

gradient furnace. Furthermore, tests of mechanical properties, as well as tests of

frost-resistance of the samples were carried out.

On the basis of primary analyses and samples prepared in a lab, it was established

that marine sediments from the Port of Koper without any additives are only

conditionally suitable as a source material for producing brick products. In

collaboration with Gorica brickworks (Goriške opekarne), a pilot production from a

mixture of 60% component B from Gorica brickworks and 40% component A

(marine sediments) from the Port of Koper was prepared. Different tests showed the

mixture could be appropriate for brick production.

Keywords: marine sediments, recycling, clay bricks, chemical analysis, mechanical

properties, brick production

II

IZVLEČEK

Transport večine trgovskega blaga po svetu poteka po morju in poglabljanje

morskega dna je bistvenega pomena za razvoj pristanišč. Ravnanje z izkopanim

materialom je zato globalni problem. Morski sediment je zaradi svoje kemijske in

mineraloške sestave primerna surovina za uporabo v opekarski industriji. Morski

sediment lahko služi kot surovina za proizvodnjo glinenih blokov, strešnikov in

keramičnih ploščic.

Da bi ugotovili, ali je bagrani material iz Luke Koper okolju prijazen in primeren za

uporabo v opekarski industriji, so bili izvedeni različni testi. Ti so obsegali: kemične

in mineraloške teste, analizo velikosti delcev in analizo vsebnosti kloridov ter

testiranje žganja v gradientni peči. Poleg tega so bile izvedene raziskave mehanskih

lastnosti in odpornosti vzorcev proti zmrzali.

Na podlagi primarnih analiz in vzorcev, pripravljenih v laboratoriju, je bilo

ugotovljeno, da je morski sediment iz Luke Koper brez kakršnihkoli dodatkov le

pogojno primerna surovina za proizvodnjo opečnih izdelkov. V sodelovanju z

Goriškimi opekarnami je bila pripravljena pilotna proizvodnja vzorcev, narejenih iz

mešanice iz 60 % komponente A in 40 % komponente B (luškega mulja). Različni

testi so pokazali, da je mešanica primerna za proizvodnjo opečnih izdelkov.

Ključne besede: morski sediment, recikliranje, opeke, kemična analiza, mehanske

lastnosti, proizvodnja opečnih izdelkov.

III

TABLE OF CONTENTS

1 INTRODUCTION ............................................................................................................................. 1

1.1 Aim, purpose and hypotheses of the Master’s thesis .................................................... 3

2 THEORETICAL BACKGROUND ......................................................................................................... 5

2.1 Description of technological processes for the production of roofing tiles and blocks

in Gorica brickworks ........................................................................................................... 10

2.2 Life Cycle Assessment – LCA......................................................................................... 13

2.3 Study area .................................................................................................................... 15

2.4 Potential sources of sediment pollution in port basins ............................................... 16

2.5 Sampling ....................................................................................................................... 18

2.6 Description of the sampling locations and samples .................................................... 19

2.6.1 Description of the location and sediment samples from the Basin 1 ................................. 19 2.6.2 Description of the location and sediment samples from the Basin 2 ................................. 20 2.6.3 Description of the location and sediment samples from the Basin 3 ................................. 21 2.6.4 Description of the reference location and sediment samples from Koper Bay ................... 21

3 MATERIAL AND METHODS ........................................................................................................... 22

3.1 Methodology ................................................................................................................ 22

3.2 Sampling ....................................................................................................................... 23

3.2.1 Sampling in Basin 1 ............................................................................................................ 23 3.2.2 Sampling in Basin 2 ............................................................................................................ 24 3.2.3 Sampling in Basin 3 ............................................................................................................ 25 3.2.4 Sampling at the reference point in Koper Bay .................................................................... 25

3.3 Chemical tests .............................................................................................................. 26

3.3.1Analysis of the pollution level .............................................................................................. 28 3.3.2 Potential use of marine sediments for the production of clay bricks ................................. 34

3.4 Methods of analyses .................................................................................................... 35

3.4.1 Chemical analysis ............................................................................................................... 35 3.4.2 Mineralogical analysis ........................................................................................................ 35 3.4.3 Particle size analysis ........................................................................................................... 35 3.4.4 The sulfate content, water-soluble and total chloride ....................................................... 36 3.4.5 Ceramic-technological tests of clay .................................................................................... 36 3.4.6 Ceramic-technological testing of a mixture containing 40% of component A and 60% component B ............................................................................................................................... 39 3.4.7 Testing modular blocks from pilot production ................................................................... 42 3.4.8 Life Cycle Assessment – LCA ............................................................................................... 44

4 RESULTS AND DISCUSSION .......................................................................................................... 46

4.1 Chemical analysis ......................................................................................................... 46

4.2 Mineralogical analysis .................................................................................................. 50

4.3 A particle size analysis .................................................................................................. 54

4.4 The sulfate content, water-soluble and total chloride ................................................ 56

4.5 Ceramic-technological tests of clay ............................................................................. 57

IV

4.5.1 Determination of clay plasticity .......................................................................................... 57 4.5.2 Results of firing in a gradient furnace ................................................................................ 58 4.5.3 Firing process at three selected temperatures (950°C, 1050°C and 1100°C) ...................... 59 4.5.4 The assessment of the resistance to freezing ..................................................................... 61

4.6 Ceramic-technological testing of a mixture containing 40% of component A and 60%

of component B .................................................................................................................. 64

4.6.1 Chemical analysis ............................................................................................................... 64 4.6.2 Mineralogical analysis ........................................................................................................ 64 4.6.3 The content of sulfates, chlorides and total salts ............................................................... 66 4.6.4 Ceramic-technological tests of clay .................................................................................... 66 4.6.5 Results of firing in a gradient furnace ................................................................................ 67 4.6.6 Preparing and testing the mixture ..................................................................................... 69 4.6.7 The assessment of the resistance to freezing ..................................................................... 70

4.7 Testing modular blocks from pilot production ............................................................ 73

4.7.1 Determining sizes, BSEN 772-16:2011 ................................................................................ 73 4.7.2 Determining the net volume and proportion of holes in bricks by weighing in water, BS EN 772-3: 1999 ................................................................................................................................. 74 4.7.3 Determining water absorption ........................................................................................... 75 4.7.4 Determining holes and net volume, as well as the percentage proportion of holes in clay and lime bricks filled with sand, BS EN 772-9:1999/A1:2005 ...................................................... 76 4.7.5 Determining net and gross density of dry bricks, BS EN 772-13:2002 ................................ 77 4.7.6 Determining compressive strength, BS EN 772 - 1:2011 .................................................... 78

4.8 Comparison of the regular production and pilot production ...................................... 80

4.9 Results of Life Cycle Assessment – LCA ........................................................................ 82

5 CONCLUSIONS ............................................................................................................................. 85

6 REFERENCES ................................................................................................................................ 87

ANNEXES ........................................................................................................................................ 95

V

LIST OF FIGURES

Figure 1: The Port of Koper. ....................................................................................... 1 Figure 2: Dredging today – cassette ........................................................................... 2 Figure 3: European experiences .................................................................................. 7 Figure 4: Primary processing - ripening. .................................................................. 10 Figure 5: Vacuum presses for tiles, a cutting table and tunnel oven for blocks. ...... 11

Figure 6: Phases of the LCA. .................................................................................... 14 Figure 7: Red dots represent the sampling points in the Port of Koper .................... 18 Figure 8: Forming the samples. ................................................................................ 37 Figure 9: Samples fired at 950°C. ............................................................................ 37 Figure 10: Samples fired at 1050°C. ......................................................................... 38

Figure 11: Samples fired at 1100°C. ........................................................................ 38 Figure 12: Shaping and drying the samples .............................................................. 41

Figure 13: Samples fired at 950oC. ........................................................................... 42

Figure 14: Chromatogram “Basin 1 - surface – S1”. ................................................ 51 Figure 15: Chromatogram “Basin 1 - surface - S1” – fraction <2 m. ..................... 51 Figure 16: Chromatogram “Basin 1 - depth - S1”. ................................................... 52

Figure 17: Chromatogram “Basin 1 - depth- S1” – fraction <2 m. ......................... 52 Figure 18: Chromatogram “Bay of Koper - depth”. ................................................. 52 Figure 19: Chromatogram “Bay of Koper - depth” - fraction<2 m. ....................... 53

Figure 20: The particle size distribution of the sample “Basin 1 - surface - S1”. .... 54 Figure 21: The particle size distribution of the sample “Basin 1 - depth - S1”. ....... 55

Figure 22: The particle size distribution of the sample “Bay of Koper - depth”. ..... 55 Figure 23: The graph shows the shrinkage and water absorption depending on firing

temperatures. ..................................................................................................... 58 Figure 24: The appearance of samples after firing in a gradient furnace. ................ 59

Figure 25: The appearance of the samples fired at 950oC after testing the resistance

to freezing. ......................................................................................................... 62 Figure 26: The appearance of the samples fired at 1050

oC after testing the resistance

to freezing. ......................................................................................................... 62 Figure 27: The appearance of the samples fired at 1100

oC after testing the

resistance to freezing. ........................................................................................ 62 Figure 28: Diffractogram of an average unfired sample. ......................................... 64 Figure 29: Diffractogram of an unfired mixture - fraction below 2 m. .................. 65

Figure 30: The graph showing the shrinkage and water absorption depending on

firing temperatures. ............................................................................................ 68

Figure 31: The appearance of the samples after firing in a gradient furnace. .......... 68

Figure 32: The appearance of samples fired at 950, 1050 and 1100oC after freezing

........................................................................................................................... 71 Figure 33: Pilot production: Brick – modular brick MB 29-19, 190 x 290 x 190 mm.

........................................................................................................................... 81 Figure 34: Environmental impacts of the MB 29-19 in its life cycle. ...................... 82 Figure 35: Normalized environmental impacts (based on the Europe 25+3

normalization) of the MB 29-19 in its life cycle. .............................................. 83 Figure 36: A relative contribution of different life cycle stages to the total

environmental impacts. ...................................................................................... 83

VI

LIST OF TABLES

Table 1: Five types of beneficial reuse of dredged material (Dreadging: The Fact) .. 8 Table 2: Life cycle phases and the system boundaries ............................................. 14 Table 3: List of standards and methods used in carrying out the chemical analysis 26

Table 4: The evaluation of the hazardous characteristics of marine sediments ........ 28 Table 5: The evaluation of the hazardous characteristics of marine sediments- H1530 Table 6: Data used in the LCA for manufacturing 1 brick. ...................................... 44 Table 7: Chemical composition of the marine sediments - Basin 1 ......................... 46 Table 8: Chemical composition of the marine sediments - Basin 2 ......................... 47

Table 9: Chemical composition of the marine sediments - Basin 3 ......................... 48 Table 10: Chemical composition of the marine sediments - Bay of Koper .............. 48

Table 11: The mineralogical composition of sediments ........................................... 50

Table 12: The particle size distribution and the moisture content ............................ 54 Table 13: The sulfate content, water-soluble and total chloride ............................... 56 Table 14: Plasticity determination ............................................................................ 57 Table 15: Plasticity classification ............................................................................. 57

Table 16: The shrinkage and water absorption depending on the firing temperature58 Table 17: The conditions of shaping the samples and the characteristics of clay after

firing and drying ................................................................................................ 60 Table 18: The assessment of resistance to freezing .................................................. 61 Table 19: Chemical composition of the mixture ....................................................... 64

Table 20: Mineral composition of the sample .......................................................... 65 Table 21:The content of sulfates, chlorides and total chlorides ................................ 66

Table 22: Determining plasticity .............................................................................. 66 Table 23: Plasticity classification ............................................................................. 66

Table 24: The shrinkage and water absorption depending on the firing temperature67 Table 25: The conditions of shaping the samples and the characteristics of clay after

firing and drying ................................................................................................ 69

Table 26: The results after determining the resistance to freezing. .......................... 70

Table 27: Determining sizes ..................................................................................... 73 Table 28: Determining the volume and proportion of holes in brick by weighing in

water ................................................................................................................... 74 Table 29: Determining water absorption .................................................................. 75 Table 30: Determining holes and net volume ........................................................... 76

Table 31: Determining net and gross density of dry bricks ...................................... 77 Table 32: Determining compressive strength (height) .............................................. 78 Table 33: Determining compressive strength (length) .............................................. 79

Table 34: Comparison between a pilot production and regular production .............. 80 Table 35: Emissions to the air (tons) for MB 29-19 in its life cycle ....................... 84

1

1 INTRODUCTION

The Port of Koper is a multipurpose port, equipped and qualified for the handling

and storage of many types of goods. It consists of three basins and two docks (see the

interactive map in Figure 1).

Figure 1: The Port of Koper (Interactive map. Luka Koper 23.2.2015).

Dredging operations are necessary to maintain navigation in waterways and access to

harbors. Each year, 100 million tons of material is dredged around the world (Dubois

et al., 2009). The current navigation channels in Koper Bay are not deep enough for

the drafts of modern transport ships (Xu et al., 2013).

According to the development strategies of the Port of Koper, a depth of -15 meters

is necessary to allow the arrival of the largest post-Panamax vessels and ameliorate

the area to new port capacities. For these reasons, navigation channels in Basins 1, 2

and 3 are planned to be deepened. When deepening the navigation channels, the

excavated material will be deposited to a predetermined location. The dredged

material of around 300.000 m3 is expected to be deposited in three cassettes located

in Ankaranska Bonifika (Krašovec, 2012).

2

A cassette has three chambers, and spillways are built at embankments. When

building a cassette, ensuring watertight peripheral embankments and watertight

bottom are of key importance, so that uncontrolled seepage of water or entry of water

through the embankment or the bottom is prevented. Figure 2 shows how dredging is

carried out today.

Figure 2: Dredging today – cassette (Likar et al., 2009).

The disposal areas available close to the Port of Koper are limited; therefore, studies

on alternative uses of the dredged material as secondary raw material for producing

clay masonry units are essential, which will be also in line with the national and

European sustainability requirements (Likar et al., 2009).

3

1.1 Aim, purpose and hypotheses of the Master’s thesis

The purposes of this study are the following:

to analyze and evaluate the marine sediments obtained by dredging Koper

Bay seabed in terms of environmental parameters and options of its further

use to avoid landfill deposits of large amounts of sediment waste;

to analyze the properties of the marine sediments (chemical-mineralogical

parameters, size of particles, carbonate content) to evaluate their potential

usability;

to prove that the dredged material (marine sediment) is suitable for producing

brick products, which will be useful in construction;

to define appropriate processes, process parameters and possible additions to

produce a product with the desired properties;

to check if the marine sediments have any dangerous substances (heavy

metals) and to analyze the extraction of hazardous substances from fired

products.

Therefore the overall aim of this research is to study the suitability of marine

sediments (provided by the Port of Koper) for producing clay bricks. Shaping,

drying, and firing behavior of marine sediment samples on mechanical properties, as

well as water absorption and frost resistance of the final product are investigated.

Along with the development of new materials and the creation of appropriate

methodology to study options of using waste materials, the proposal presented will

definitely contribute to science significantly by contributing to the environmental

sciences by assessing marine sediment regarding its environmental impacts (both

through the chemical analysis as well as by means of LCA) and by providing

potential solution for its re-use.

The goal of the LCA study was to identify the environmental impacts of the newly

developed product – a modular brick MB 29-19 in its all phases of a life cycle

(production, usage, and final reuse) in order to get information about its impacts and

possible improvements in the production phase as well as giving information to the

decision-makers and potential consumers.

4

Hypotheses which are addressed in the present work are:

1. The marine sediments from the port of Koper are inert or non-dangerous in

terms of their chemical composition and can be further used.

2. The marine sediments alone or in combination with other material can be due

to its chemical and mineralogical compositions as well as due to the particle

size used in construction sector, especially for the for brick production.

3. The products (bricks) based on the marine sediments meet the requirements

of sustainable production from the perspective of LCA (Life Cycle

Assessment).

The project is also supported by the company Luka Koper, d.d., where a volume of

300.000 m3 dredged material is expected to be obtained. The disposal of this material

is a significant financial and environmental burden for the company, which will be

(at least partially) solved by this research.

5

2 THEORETICAL BACKGROUND

Dredged material can be a valuable resource although much of it is currently

disposed because of economic, logistical or environmental constraints. In many

countries, disposal is getting more and more difficult due to a lack of disposal areas

as well as environmental concerns. Therefore, the interest in alternatives is growing,

especially the potential to use dredged material as raw material (Lindsay, 2008).

Most dredged material can be used directly underwater or on land after dewatering.

Potential contamination, however, does not rule out the possibility of using the

dredged material, depending on site-specific conditions and legislation.

Contaminants can be stabilized or removed by various treatment techniques to make

it suitable for its further use. It should be noted, however, that any treatment or

handling steps increase the overall costs of recycling the dredged materials for

secondary uses (Bortone and Palumbo, 2007).

The deepening of the seabed is important to ensure adequate depths of navigation

channels and waterways at docks, as required by drafts of cargo ships. The

maintenance of the bay seabed is carried out with a dredger. In the sea and

freshwaters, sediments accumulate on the bottom. The rate of the accumulations of

deposits depends mainly on the volume of sediments brought by watercourses, sea

currents, erosion, and other physical and natural phenomena (Mazen et al., 2009).

In water areas where various activities take place, such as in a port, the accumulated

sediments become disruptive and must be removed. Therefore, it is expected a great

volume of dredged material to be always available in the area covered by the port of

Koper. Recently, the practices of managing marine sediments after dredging have

become increasingly complex (Sheehan 2012).

When deciding how to treat and use dredged material, it is crucial to evaluate its

geomechanical and environmental properties. The sediments obtained by dredging

are mainly composed of sand, clay fraction and seawater, and can also include

contaminants with a range of hazardous properties (Mezencevova et al., 2012).

6

The discharging of sediments into a water body leads to an accumulative rise of

aluminum concentrations in water, aquatic organisms, and, consequently, in human

bodies (Prakharand and Arup, 1998).

Marine sediment accumulation has intrinsic risks for the health of workers, and

sediment management should be done by caution, using protection devices described

by EU regulations, to avoid contamination of the working environment and to limit

the exposure to contaminants of the workers in this sector.

Marine sediments are a good indicator of marine pollution, as pollutants accumulate

in sediments over a longer period of time. In Slovenia, there are several regulations

covering the management of mineral waste (direct or indirect), which are under

control of the Environmental Protection Act. For this study, the most important

national regulation is the Decree on Waste Management, arising from construction

contracts. In this regulation, the dredged material belongs to the class of construction

waste (group 17, subgroup of 17 05, in the series of 17 05 05* and -06; hazardous

and non-hazardous form). The dredged material from marine sediments is generally

non-hazardous waste, but it can be dangerous due to the presence of pollutants from

port operations (Krašovec, 2009).

Dredging equipment, classified according to the methods of excavation and

operation, can be grouped into the following main categories:

- mechanical dredgers;

- hydraulic dredgers;

- special, low-impact dredgers, and

- other types of dredgers.

Increasingly strict environmental regulations have led to significant developments in

dredging equipment. These include automatic control, positioning systems and

degassing systems. These innovations aim to reduce potentially adverse

environmental impacts (dredging: The facts).

7

When dredged material is to be deposited on land or used for beneficial purposes, it

is necessary to process it technologically. The rate of technological treatment

depends on the purpose of use. The world has many technological processes, where

dredged material is separated by fractions and processed to the extent that it is useful

for various purposes. Figure 3 shows the most used methods of processing or using

dredged material as raw material in some European countries (Likar et al., 2009).

Figure 3: European experiences (Likar et al., 2009).

“The focus is on working-with-nature solutions for the beneficial re-use of dredged

material. A working-with-nature solution for the beneficial reuse of sediment is a

solution whereby the sediment or dredged material is used locally, preferable in the

system, and use is made of natural processes to distribute the sediment (tides, waves

etc.) or to trap additional sediment (reed, oysters, etc.). When we can realize these

sustainable solutions, sediment is experienced as a (local) resource instead of a

threat. A win-win solution with costs savings, reduction in CO2 and where possible,

nature development is obtained. Five types of beneficial re-use of dredged material

are provided in the table below. These types of measures meet the conditions of local

use of dredged material and the use of natural processes (tides, waves, geochemical

and geophysical processes etc.)” (The beneficial reuse of dredged material).

8

Table 1: Five types of beneficial reuse of dredged material (Dreadging: The Fact)

Types of beneficial

re-use of dredged

material for:

Description of the measure Examples

A. Sustainable

relocation in the

estuary

Dredged material is re-placed in the estuary by means of

natural processes (tides, currents, sediment transport) the

sediment is distributed to the intertidal mudflats and salt

marshes. This way the necessary deepening of the shipping

channels is combined with enhancing the natural value of the

estuary, while keeping transport costs of the dredged

material low because of local re-use.

Western Scheldt, NL

Waddensea, NL

Mersey Estuary, UK

Lower Orwell, UK

In-Harbor placement,

Poole, UK

B. Erosion control

by salt marsh and

foreshore

replenishment

Dredged material is placed directly on the foreshore,

enhancing salt marshes’ ability to act as a buffer against

wave energy.

Lake IJsssel, NL

Lymington, UK

Horsey Island, UK

Eastern Scheldt, NL

C. Erosion control

by beach

nourishment

Dredged material is placed directly on the beach to support

the natural wave attenuation function.

Poole, UK

Horsey Island, UK

D.Riverbank erosion

control by reed bed

reinstatement

Geotubes, filled with dredged material, are placed to protect

river banks again erosion. Locally-sourced reed is planted in

or behind the geotubes (and/or by natural growth). The reed

reduces wave energy and protects the river banks, while at

the same time trapping sediment, thereby further

strengthening the river banks while lowering the sediment

reflux to the river.

Salhouse Broad, UK

Duck Broad ,UK

RingvaartHaarlemmerm

eer (NL)

E. Ripening of

dredged material

Ripening of dredged material is a natural dewatering or

’drying' process. Raw dredged material transforms into soil

influenced by chemical and physical processes. The aim of

ripening is to obtain clay or soil which complies with

environmental legislations and geotechnical specifications

for application in earthworks (e.g. dikes, noise reduction

banks, landfill covers). Ripening is applied in rural areas on

a small scale and mainly for clean or lightly contaminated

dredged material from regional waterways. The obtained

clay or soil is locally used to raise the land.

Many agricultural fields,

forelands, NL

9

Dredging can be undertaken to benefit the environment in several ways. Dredged

materials are frequently used to create or restore habitats. Recent decades have also

seen the increasing use of dredged materials for beach replenishment. These schemes

are designed to prevent or reduce the likelihood of erosion or flooding. Such beach

nourishment or recharge is achieved by placing dredged sand or gravel on eroding

beaches. This represents a “soft-engineering” solution, an important alternative to –

often more costly – structural solutions such as rock armor or concrete walls.

Another environmental use of dredging has been designed to remove contaminated

sediments, thus improving water quality and restoring the health of aquatic

ecosystems. This so-called “remediation” or “clean-up” dredging is used in

waterways, lakes, ports and harbors in highly industrialized or urbanized areas. The

removed material may be treated and used afterwards, or disposed of under strict

environmental controls. Under proper conditions a viable alternative to removal is in-

situ isolation, i.e. the placement of a covering or a cap of clean material over the

contaminated deposit (Dredging: The Facts).

Considerable large quantities of marine sediments are frequently land-filled although

they could be used as a non-expensive substitute for raw materials in the ceramic or

clay-based industry (Krašovec, 2009).

Brick is one of the most important construction elements. The history of brick

production goes back 8000 years when the fabrication of the earliest sun dried clay

bricks was discovered. The sediments generated at water treatment plants should be

treated and handled in an environmentally friendly manner. Coagulant sediments are

generated by water treatment plants, which use metal salts such as aluminum sulfate

or ferric chloride as a coagulant to remove turbidity. The traditional practice of

discharging the sediments directly into a nearby stream is becoming less acceptable

because these discharges can violate the allowable stream standards (Sullivan et al.,

2010).

10

2.1 Description of technological processes for the production of roofing tiles and

blocks in Gorica brickworks

In the primary preparation stage, the raw material needs to be properly mixed,

crushed, cleaned, moistened, dried and grounded to the required granulation. Scoping

of clay at the landfill is carried out by a loader, which is used for transport and

loading into a trunk feeder, which uses a throttle device to feed on a rubber conveyor

in the correct quantity ratio. With a conveyor rubber band the raw material and

additives are transported to a grinding wheel, where they are moistened with a

dosage of water, if necessary. Further transport is performed through rubber transport

bands into a rough roller mill for rough grinding and from here through rubber

transporters into a fine roller mill, where the raw material is finally grounded to a

desired thickness. The raw material is further transported through a rubber

transporter into a half-opened ripening chamber (see Figure 4).

Figure 4: Primary processing - ripening (Gorica brickworks).

The ripening chamber is used for accumulation, homogenization and ripening of the

prepared raw material. The raw material for tiles or blocks matures on different piles.

From here on, we have two separate lines – one for the production of roofing tiles

and the other for the production of blocks. For the production of tiles, homogenized

and moistened raw material is excavated with the help of a bucket-wheel excavator

and transported with rubber bands to the rough roller mill, where the dried raw

material is further grinded and continues to the sieve homogenizer using

homogenization, the final automatic correction of humidity and uniform adding into

biaxial mixer of a vacuum press. A similar system is used for the production of

blocks. From here, the homogenized and moistened raw material is carried using a

bucket-wheel excavator from the ripening chamber, through the rubber bands to

11

screw feeder for dosing of sawdust into the sieve homogenizer and into biaxial mixer

of a vacuum press.

Design of blocks and tiles is carried out by extrusion, using a vacuum presses, which

consist of a mixer and an extruder. In the production of tiles, the biaxial mixer of the

vacuum press mixes feed raw material and at the end pushes it using screws through

chopping knives into a vacuum chamber. In the production of blocks, screws push

the raw material into a vacuum chamber through bars. From here, the raw material

falls on the injection pumps, which push the clay into screw spiral which continues

pressing it through the exit of the extruder, where is a tool that gives the form to

products.

On the cutting table for blocks and tiles, the material is cut to the required length and

shape. On the roller transporter, raw packages are formed, which are loaded on the

drying shelves and then into the drying rack using a lift. Full drying racks are driven

into draying chambers using a semi-automatic transporter or an automatic transporter

for further drying of products. After the cut, the excess raw material is returned

through rubber transporters to the sieve homogenizer, where it is re-mixed and

pressed into a biaxial mixer of the vacuum press.

Figure 5 shows vacuum presses for tiles, a cutting table and tunnel oven for blocks.

Figure 5: Vacuum presses for tiles, a cutting table and tunnel oven for blocks (Gorica brickworks).

Drying is discharging of water from raw-designed products. Drying is divided into

three stages. The purpose of the first stage is to achieve slow discharge of water from

the surface layer and thereby reduce humidity gradient across the entire cross-section

of the material. This reduces the possibility of deformation and damage. By

eliminating water from the material, material shrinks and thus narrows the ways for

discharging water from the product`s interior. The third stage begins when the

12

product is reduced to the final size. Now, air at high temperatures and speeds and low

humidity may be injected.

Drying of blocks is carried out in 10 drying chambers. Dry and hot air, which is

obtained as a residue from cooling of material in a furnace, is pressed through the fan

and the pipelines into individual cells. During inflaming of air in the drying process,

air is drying products, acquiring moisture, becoming heavier and, due to overpressure

in the cell, going up through the floor vents and channels into the chimney and the

atmosphere.

Tiles are dried in thirteen drying chambers. Hot and dry air, which is mainly drawn

from the tunnel furnace, is obtained by cooling the fired material, walls and ceiling

of the furnace and wagons under the furnace, and by recovering the flue gas and

preheating chamber. In the process, moisture from the clay is extruded and the

products gain the necessary strength for handling in the processes of folding and

loading on the furnace wagons. Moist air is released from the cell through the floor

channel into the chimney and the atmosphere. Once drying is completed, by means

of semi-automatic transport trolley, the drying racks with the dried material are

transported to the line for unloading from the drying shelves, where they are also

unloaded.

The firing process is carried out in a tunnel furnace in an oxidizing atmosphere, into

which wagons with material are pushed at certain intervals. The firing process is

divided into a preheating stage, a firing stage at a temperature appropriate for the raw

material and a material cooling stage. In the firing process, the product gets the final

physical and technical characteristics required of brick products. The temperature of

firing is about 1000°C. As fuel natural gas is used, which is supplied through the gas

metering and regulation station. In the process, which lasts from 35 to 60 hours,

products get a nice brick color (Gorica brickworks).

13

2.2 Life Cycle Assessment – LCA

Life Cycle Assessment – LCA is a process of evaluating the environmental burdens,

resulting from various processes, such as production/manufacturing of products

and/or provision of services. The environmental burdens are determined on the basis

of the identification and quantification of energy consumption and materials and

waste generated. The method also allows the evaluation of environmental impacts

and evaluation of opportunities with the aim to improve the state of the environment.

The assessment usually encompasses the entire life cycle, from the extraction of raw

materials, input materials, production, transport and distribution, use and reuse,

maintenance to recycling and final disposal in the environment (Setac, 1991).

LCA is composed of 4 phases (see Figure 6):

1. Goal and scope definition

2. Inventory analysis

3. Impact analysis

4. Interpretation of results

The technique used in the LCA is modeling. In the phase of inventory analysis, a

model is formed, consisting of a complex technical system, which is used for

production, transport, use and disposal. The result is a flow sheet or a process tree.

For each process, it is necessary to collect all the inflow and outflow data. In

assessing the impact on the environment, the various models that describe the

adequacy of inflows and outflows are used. The result is introduced as a several

categories of impact, such as climate change, ecotoxicity, etc.

14

Figure 6: Phases of the LCA (PRé Consultants, 2006).

LCA used in this study is based on the standards ISO 14040 in 14044 (ISO 2006 a,

b). For modeling, a software program GaBi 4 Professional® (PE International, 2008)

and data-based Ecoinvent v2.1 (Frischknecht et al., 2007) were used.

The functional unit describes and quantifies those properties of the product, which

must be present for the studied substitution to take place. These properties (the

functionality, appearance, stability, durability, ease of maintenance etc.) are in turn

determined by the requirements in the market in which the product is to be sold

(Weidema et al., 2004). A functional unit is defined as a production of 1 modular

brick with a life span of 100 years, used for building purposes.

Table 2shows the considered life cycle phases and the system boundaries. The study

encompasses the production phase, usage phase and the product's end phase, where a

material reuse is to be considered.

Table 2: Life cycle phases and the system boundaries

Production Construction and use End-of-life

Raw material production

Transport

Manufacturing (e.g. drying,

firing, cooling…)

Transport

Installation

Transport

Waste processing//reuse as

aggregates

15

2.3 Study area

The management of the whole Koper Bay is an environmental priority, mainly done

by Luka Koper, d.d. Its work makes it possible to monitor and implement the

protection system at all terminals and in all its activities. With the help and

inspection from the presiding expert institutions, the company regularly monitors

chemicals and noise emissions. The company has implemented plant-escaping

strategy from the port area. The company systematically manages waste in

accordance with waste management policies. It has introduced a separate collection

of waste deposits and recycling strategies. Also, a modern waste management center

has been built. The quantity of unusable waste has decreased considerably, and the

working environment has improved, along with higher productivity and more cost-

effective operations. Today, more than 70% of all waste produced in the port is

collected separately and sent to recycling. The environment management system

involves all employees, who are regularly trained in the field of environmental

monitoring. The Environmental Manager attends international seminars and

conferences as well (Environmental friendly policy).

Marine sediments are a good indicator of pollution in the sea, because the pollutants

are deposited in sediments over a long period of time. Elevated levels of certain

pollutants in the marine sediments in the Port of Koper may arise directly as a

consequence to their own activities as well as external influences. The Port of Koper

is aware of the impacts that port activity has on the environment. Monitoring and

managing the environmental impact has become a part of regular activities. The port

has an organized management system for many years now. The port has to respond

to incidents, mainly caused by oil pollution, coal dust, inadequately purified sewage

of the wastewater treatment plant of Koper and other various sediments, which are

washed by the Rižana River and other streams.

There are about 200 different companies whose activities can have a significant

impact on the quality of the environment in the port. The environmental situation in

the Port of Koper is also influenced by natural characteristics of the surrounding

harbor. The Rižana River flows in the port carrying a high content of suspended

16

particles, which makes the bottom of the Basin 2 muddy. Ocean currents also

contribute to the continuous application of the material in all harbor basins. Near the

port, there is a nature reserve, classified as Natura 2000 network. It is a

Mediterranean wetland, well-known for its rich fauna and flora. This is also the

largest brackish wetland in Slovenia. There are another two areas classified as Natura

2000 network. There are a swamp of Saint Nicholas, known for its rare salt-marsh

vegetation, and a unique meadow of Posidonion oceanicae in Žusterna (Justin et al.,

2014). Posidonion oceanicae is sea grass characteristic for the North-Adriatic Sea, in

Trieste Bay it can be found near Grado in Italy and in a small area (1 km) along the

Slovenian coast between Koper and Izola (Ruggiero et. al., 2002).

2.4 Potential sources of sediment pollution in port basins

The marine sediments may include waste arising from maritime transport, like ship

ropes, strapping for packaging, tarry residues, packaging of oil and gas and

packaging of food and cleaners. Other types of waste, which may appear on the

bottom of the sea, are caused by fisheries, tourism and recreation. These sectors

leave behind nets for shellfish farming, fishing nets, monofilament ropes, floats,

pieces of Styrofoam, polystyrene boxes, baits, food packaging, cigarette butts, wastes

of the maintenance of vessels, packaging for cosmetics, sunglasses, swimming

equipment, etc. Furthermore, the marine stream may also carry them into the Port of

Koper (Stanič Racman, 2013).

The pollution in the port is caused by vessel traffic and industrial waste water.

Marine sediments are formed due to a wide range of activities, such as production

and processing activities, construction, trades and maintenance of motor vehicles, the

transshipment and freight forwarding, catering industry, hospitality industry, hospital

and specialist medical activities and, in the field of waste management, as a

consequence of leaching from illegal landfills, agricultural operations and cross-

border pollution. Establishments that produce industrial wastewater polluted with

various pollutants are located along the entire coastal strip and in the Rižana,

Badaševica and Drnica Rivers. Pollutants are also active substances used in

agriculture and the most polluted areas include the marine environment of Koper and

17

Piran Bays and the Rižana River. The sources of marine pollution and marine

sediments are certainly not negligible either (Stanič Racman, 2013).

It is also possible that it comes to incidental pollution caused by accidents involving

dangerous chemicals in industrial establishments and accidents in the transport of

dangerous substances, which can cause sea pollution directly or via rivers flowing

into the sea (Stanič Racman, 2013).

Due to the maritime transport, there is a risk of increasing sea pollution of the sea

and coastline in the entire northern Adriatic area. Depending on the type of pollution,

the traffic sources can be divided into (Stanič Racman, 2013):

- Cargo oil, transported to or from the port of Trieste;

- Crude oil and other hazardous substances;

- Cargo oil and derivatives, transported to the port of Koper;

- Cargo transport of chemicals and special loads to or from the port of Koper;

- Discharging waste oil from ships, transported to or from the port of Trieste or

Koper.

The most critical aspect of the sea pollution with far reaching effects on the whole

environment is oil spills. When the oil or its derivatives flow into the sea, they form

oil slick on the water surface. Light particles evaporate quite rapidly, and as the oil

slick spreads the evaporation of particles accelerates even more. Heavier oil particles

of a higher density may sink to the bottom, but this is mainly only common in places,

where fresh and salt water are mixed and the sea water is of lower density. After a

few hours, the primary oil slick begins to decompose, mainly due to ocean currents

and waves. The slick spreads depending on the wind and sea currents, and on the

temperature, tidal and wind speed. Oil slick moves on the water surface in the

direction of the wind with 3–4% velocity. In confined waters, water currents and

tides have a strong influence on the moving of the oil slick (Justin et al., 2014).

Water-soluble components in the water column gradually degrade (dissolution), the

rest of the particles emulsify and disperse in the water column as small drops. The

emulsion of water and oil, resulting in the process of emulsification is due to its

18

composition strongly resistant. Oil in water also reacts with oxygen, which is called

the oxidation process. This forms tar and the sunlight accelerates the process. An

important factor in the self-cleaning ability of the sea is ultimately marine

microorganisms, which are able to break down the oil in the water-soluble

components and eventually to carbon dioxide and water (Justin et al., 2014).

2.5 Sampling

The port of Koper comprises three basins and two docks, where loading, unloading

and warehousing take place. A team of divers took samples of marine sediments in

all three basins and an additional sample at a reference point in Koper Bay. Samples

were taken between 8th and 11th of March 2014. In each basin, four samples were

taken at two depths, where the deepening of the basins will be carried out; two

samples were taken at a depth toward the shore and two samples at a depth toward

the sea, and two samples at a reference point in Koper Bay. A total of 56 samples in

a total quantity of 300 liters were taken. Figure 7 shows the sampling point of Koper.

Red dots show the locations where the sample marine sediments were taken (Justin et

al., 2014). The sediment samples are shown in Annex 1.

Figure 7: Red dots represent the sampling points in the Port of Koper (Justin et al., 2014).

19

To avoid contamination of the samples and to prevent a change in specific physical

and chemical properties of the samples, during transport and until the beginning of

the chemical and physical tests, the samples were appropriately (Justin et al., 2014):

Packed: The samples to determine inorganic parameters as well as physical

parameters were packed in white plastic buckets. And the samples to

determine the organic parameters were packed in glass cassettes. To

minimize the air content in the cassettes, the samples were filled to the top

and tightly sealed;

Marked and labeled with waterproof marker pens and stickers; and

Stored: Once the samples were taken, packed and marked, they were then

cooled to a temperature of 4 2 C and kept in the dark.

2.6 Description of the sampling locations and samples

Samples are apparently different from one basin to another. In particular from the

Basin 2, where is a noticeable visual impact of the Rižana River and probably of the

central wastewater treatment plant. In addition, the structure of the sediments was

different from one location to another. Depending on the seabed and marine life, the

visual assessment of the reference point was appropriate (Justin et al., 2014):

2.6.1 Description of the location and sediment samples from the Basin 1

a. Location towards the coast (sample 1 – surface and depth)

- Description of the sample location: The sea bottom is muddy. The signs of

surface material removed are visible, most likely due to the ships engines

running.

- Description of samples: samples taken from the depth and surface towards the

coast of the first basin visually represent light grey sediments with ocher

stains, odorless and without other anthropogenic inclusions. Samples are on

touch clayey.

b. Location towards the sea (sample 2 – surface and depth)

- Description of the sample location: The sea bottom is muddy.

20


sea of the first basin visually represent light grey sediments with ocher stains,

odorless and without other anthropogenic inclusions. Samples are on touch

clayey.

The marine sediment samples are at both locations of the basin1the hardest,

compared with other sampling locations. In the sediments, shells of marine

organisms are found.



- Description of the sample location: The sea bottom is muddy. The bottom is

soft. According to estimates the sediments are disposed from the Rižana

River.


coast of the second basin visually represent the sediments of black color, with

a distinct odor of feces and contain anthropogenic inclusions of undefined

waste that resemble to pieces of cords, Styrofoam ...


- Description of the sample location: The sea bottom is muddy. The bottom is

soft.


sea of the second basin visually represent light grey sediments with a green

tint and with inclusions to burgundy ocher-red color, without odor.

Anthropogenic and natural organic admixtures in the samples were not

detected. Samples are on touch clayey.

21



- Description of the sample location: The sea bottom is muddy. At the bottom

there are signs of deepening. Furthermore, there are also visible signs of

surface material removed, most likely due to the ships engines running.


coast of the third basin visually represent light grey sediments with ocher to

burgundy red stains, odorless and without other anthropogenic or natural

organic inclusions. Samples are on touch clayey.


- Description of the sample location: The sea bottom is muddy. At the bottom

there are signs of deepening.

- Description of samples: A sample taken from the surface towards the sea at

the location of the third basin visually represents light grey sediments with

black spots, odorless and without other anthropogenic or natural organic

inclusions. The sample on touch is clayey. A sample taken from the depths

towards the sea at the location of the third basin visually represents light grey

sediments with green tint and black stains, odorless and without other

anthropogenic or natural organic inclusions. The sample is on touch clayey.

2.6.4 Description of the reference location and sediment samples from Koper Bay

- Description of the sample location: The sea bottom is muddy. It looks intact.

It is a typical intact bottom of Koper Bay.

- Description of samples: samples taken from the depth and surface at the

location of Koper Bay visually represent light grey sediments with a green

tint and ocher stains, odorless and without other anthropogenic inclusions.

There is a presence of natural inclusions shells of crabs and snails. Samples

are on touch clayey.

22

3 MATERIAL AND METHODS

3.1 Methodology

In order to study the suitability of marine sediments (from Koper Bay provided by

the Port of Koper), their content is analyzed to check its content of clay, to verify its

suitability for brick production. In accordance with the practice in the brick industry,

this phase includes the following tests:

- A chemical analysis (for the evaluation of SiO2, Al2O3, Fe2O3, CaO, MgO,

Na2O, K2O, TiO2): the composition will be determined following the BS EN

196-2 method using the X-ray fluorescence spectrometry (WD XRF) of the

manufacturer ARL 8480S. This European Standard specifies the methods for

chemical analysis of cement;

- A mineralogical analysis: the composition will be determined using Philips

Norelco equipment for X-ray diffraction analysis by means of CuK

radiation and a nickel filter. X-ray powder diffraction is a rapid analytical

technique primarily used for phase identification of a crystalline material and

can provide information on unit cell dimensions. The analyzed material is

finely ground, homogenized, and average bulk composition is determined;

- A particle size analysis: the texture of the material will be determined

according to the BS EN 933-1 standard. This European Standard describes

the reference washing and dry sieving method, used for type testing and in

case of dispute, for determination of the particle size distribution of

aggregates;

- The chloride content (Cl-) will be determined by the BS EN 196-2:2013

method and the sulfate content will be determined gravimetrically according

to the BS EN 196-2:2013 procedure. This European Standard describes

cement and concrete technology, chemical analysis and testing, determination

of content, testing conditions, calibration, construction materials.

23

Furthermore, the following ceramic-technological tests of clay are carried out:

- The preparation of the material on a vacuum extruder (plasticity

determination using Pfefferkorn method). The Pfefferkorn method determines

the amount of water required to achieve a 30% contraction in relation to the

initial height of a test body under the action of a standard mass (Pfefferkorn,

1924);

- The analysis of firing in a gradient furnace;

- The analysis of the result after a firing process at two selected temperatures

(950°C and 1100°C),

- The determination of linear shrinkage, water absorption, compressive and

flexural strengths of samples fired at selected temperatures;

- The test of the resistance to freezing of the obtained bricks (samples)

produced following the BS EN 539-2:2013 method (i.e. the water absorption

test will be carried out by submerging the brick products in water by 1/4 of its

length per 1 hour until fully submerged, afterwards holding for 24 hours.

After that, samples will be exposed to freezing–thawing cycles).

3.2 Sampling

3.2.1 Sampling in Basin 1

Sampling was conducted at two locations, one towards the shore and the other

towards the sea, at each location at two depths (Justin et al., 2014):

a. Sampling towards the shore B1S1S (basin1/sample1/surface) and B1S1D

(basin1/sample1/depth)

The depth of the sea: 12.6 m.

The quantity of samples taken:

- 12L of samples for chemical tests and 10L of samples for physical and

mineralogical tests were taken at 10cm of the sediment upper layer.


mineralogical tests were taken at 100cm of the sediment depth.

24

b. Sampling towards the sea B1S2S (basin1/sample2/surface) and B1S2D

























25






















3.2.4 Sampling at the reference point in Koper Bay

Sampling at two depths BK1S1S (Bay of Koper/sample1/surface) and BK1S1D(Bay

of Koper/sample1/depth) (Justin et al., 2014):


26






3.3 Chemical tests

Chemical tests on sediment samples from the Port of Koper basins and Koper Bay

were carried out in the labs of the Velenje Institute and SGS Slovenia. Both

laboratories are accredited according to the BS EN ISO / IEC 17025. The methods

used are listed below in Table 3 (Justin et al., 2014).

Table 3: List of standards and methods used in carrying out the chemical analysis

Parameter Standard The method of analysis

Sediments

Leaching BS EN 12457-4: 2004 24 hour leach with water; the

ratio L/S=10 l/kg

Preparation of samples BS EN 15002:2006

Dry substance (made on

fresh sample)

BS-TS CEN/TS 15414-2: 2010 Gravimetric analysis

As, Pb, Cd BS EN ISO 17294-2: 2005 mod. ICP-MS

Hg ISO 16772: 2004 AAS - hydride technique

Mineral oils BS EN 14039: 2004 GC/FID

Phenolic substances -

total

BS ISO 6439 – Method B: 1996 Spectrophotometry

BTX - volatile aromatic

hydrocarbons

BS ISO 11423-1: 1998 GC/MS

PAHs - polycyclic

aromatic hydrocarbons

BS 13877: 1999 mod. GC/MS

PCB - Polychlorinated

biphenyls

BS 10382: 2002 mod. GC/ECD

PCDDs/PCDFs - -

POX - -

TOC - Total organic

carbon

BS EN 13137: 2002 IR detection

(continues on the next page)

27

Sediment leachate

pH ISO 10523: 2008 Potentiometric

Specific electrical

conductivity

BS EN 27888: 1998 Conductometry

DOC -Dissolved organic

carbon

BS ISO 8245: 2000 IR detection

Ag, As, Ba, Be, Cd, Co,

Cr, Cu, Mo, Ni, Sb, Se,

Sn, Pb, V, Zn

B, Tl, Te

BS EN ISO 17294-2: 2005

BS EN ISO 17294-2: 2005 modified

ICP-MS

Hg BS 5666-5: 2000, chapter 5 AAS - hydride technique

Total dissolved solids BS EN 15216: 2008 Gravimetric analysis

AOX BS ISO 9562: 2005 Incineration, coulometry

Cr(VI) BS ISO 11083:1 996 Spectrophotometry

Sulfide BS ISO 10530: 1996 modified Spectrophotometry

Fluoride BS 10304-1: 2007 IC

Ammonium nitrogen BS ISO 5664 IC

Nitrate Nitrogen ISO 10304-1: 2007 IC

PAHs - polycyclic

aromatic hydrocarbons

BS EN ISO 17993: 2004 mod. MS/ECD

Cyanide - total BS EN ISO 14403-2: 2013 Spectrophotometry

Phenols ISO 14402: 1999(E) Spectrophotometry

Mineral oils BS EN ISO 9377-2: 2001 GC/FID

28

3.3.1Analysis of the pollution level

Tests of the pollution level were conducted to determine the potential hazardous

properties of the samples. Tables 4 and 5 show a comprehensive evaluation of the

hazardous characteristics of sediments from the Port of Koper. (Justin et al., 2014)

Table 4: The evaluation of the hazardous characteristics of marine sediments

Description of hazardous

characteristics

Findings - Evaluation of hazardous characteristics of sediments

H1 – explosive No

H2 – oxidizing No

H3-A –inflammable No

H3-B -highly flammable No

H4 – irritant No - sediments in contact with the skin don't cause

inflammation.

H5 – harmful No - on the basis of the measured values the samples did not

contain 25 % of one or more of the substances that harm our

health, according to the regulations in the field of chemicals.

H6 – toxic Sediments are not toxic; the basis of measured values should

not contain 0.1% or more of one or more highly toxic

substances, according to the regulations in the field of

chemicals.

Sediments also should not include 3% or more of one or

more substances classified as toxic, according to the

regulations in the field of chemicals.

H7 – carcinogenic Sediments are not carcinogenic; the sediments should not

contain 0.1% or more of one or more highly carcinogenic

substances in the 1 or 2 category, according to the

regulations in the field of chemicals.

H8 – corrosive Sediments are not corrosive; they should not contain 1% or

more of one or more highly corrosive substances classified

as R35. Furthermore, the sediments also should not contain


29

5% or more of one or more highly corrosive substances

classified as R34, according to the regulations in the field of

chemicals.

H9 – infective Sediments are not infective; they should not contain health

threatening substances and they also should not contain

infectious material of animal origin.

H10 –reprotoxic Sediments are not reprotoxic; they should not contain 0,5%

or more of one or more highly reprotoxic substances in the 1

and 2 category, classified as R60 or 361, according to the

regulations in the field of chemicals. Furthermore, the

sediments also should not contain 5% or more of one or

more substances in the 3 category, classified as R62 or R63,

according to the regulations in the field of chemicals.

H11 - mutagenic Sediments are not mutagenic; they should not contain 0,1%

or more of one or more mutagenic substances in the 1 and 2

categories, classified as R46, according to the regulations in

the field of chemicals. The sediments also should not contain

1% or more of one or more mutagenic substances in the 3

category, classified as R40, according to the regulations in

the field of chemicals.

H12 - / It is estimated that sediments do not emit toxic gases in

contact with air , water or acid.

H13 – sensitizing Sediments with inhalation or with penetration in the skin do

not induce hypersensitivity reactions.

H14 –ecotoxic We assume that the sediments are not ecotoxic; according to

the regulations for the transport of dangerous goods by road,

they should not contain ozone-depleting substances or goods

which are classified in the 9 category and assigned to UN

No. 3077 and 3082.

30

Table 5: The evaluation of the hazardous characteristics of marine sediments- H15

Description of hazardous

characteristics

Findings - Evaluation of hazardous characteristics of

sediments

H15 – /

The measured values do not exceed the prescribed limits, in

accordance with the Regulation on waste, Official Gazette of

RS, no. 103/11.

PARAMETER UNIT LIMIT RANGE OF MEASUREMENT3

The parameter values in the solid waste

Mercury mg/kg s.s. 20 0.10 – 0.53

Arsenic mg/kg s.s. 5.000 15.3 – 26.9

Lead mg/kg s.s. 10.000 21.7 – 40.2

Cadmium mg/kg s.s. 5.000 <2.0

PAHs mg/kg s.s. 100 <0.101

PCBs mg/kg s.s. 100 <0.102

PCDDs/PCDFs 10.000 ng

TE/kg s.s. 10.000 <500

Mineral oils mg/kg s.s. 20.000 <50 - 245

POX mg/kg s.s. 1.000 <104

BTX mg/kg s.s. 500 <0.04

Phenols mg/kg s.s. 10.000 <20

The parameter values in the leachate waste

Drying radical mg/l 10.000 2.330 – 4.890

pH / 6-13 8.0 – 8.6

Antimony mg/l 5 0.002 - 0.004

Arsenic mg/l 5 0.003 - 0.007

Copper mg/l 10 <0.001 - 0.004

Barium mg/l 50 0.003 - 0.007

Beryllium mg/l 0.5 <0.001

Boron mg/l 100 0.63 - 1.84

Zinc mg/l 100 0.002 - 0.012

Cadmium mg/l 0.5 <0.001

Cobalt mg/l 10 <0.001

Tin mg/l 100 <0.001

Full chrome mg/l 50 <0.005

Chromium -

Hexavalent mg/l 2

<0.05


31

Nickel mg/l 50 0.002- 0.011

The sum of selenium

and tellurium mg/l 5

<0.030

Silver mg/l 5 <0.001

Lead mg/l 10 <0.001

Thallium mg/l 2 <0.001

Vanadium mg/l 20 0.004 – 0.036

Mercury mg/l 0.05 <0.001

Ammonium nitrogen mg/l 1.000 <1.0 – 5.3

Nitrate nitrogen mg/l 30 <30

Cyanide - total mg/l 20 <0.005

Cyanide - free mg/l 2 Not measured5

Sulphide mg/l 20 <0.04

Fluoride mg/l 50 <1.0

Mineral oils mg/l 100 <10

PAHs mg/l 0.05 <0.001

AOX mg/l 10 <0.010 – 0.056

- Phenols - mg/l - 100 - <1

- Note1

The sum of the following PAHs: fluoranthene, benzo (a) pyrene, benzo (b)

fluoranthene, benzo (k) fluoranthene, benzo (g, h, i) perylene and indeno (1,2,3-cd)

pyrene.

- Note 2 The sum of the following PCBs: 28, 52, 101, 138, 153 and180.

- Note 3 Area of the results obtained from sediments.

- Note 4

On the basis of the EOX content in a solid sample (the area of the

measurement is <0,5 mg/kg s.s.)POX content in a solid sample cannot exceed the

limit value.

- Note 5

Based on the content of total cyanide in the leachate, it can be assumed that

the content of free cyanide does not exceed the limit.

The key environmental risk of the dredged material to the environment is its content

of hazardous substances (H13). Only relevant (heavy metals) were identified in

sediments while the organic substances were not (Likar et al., 2009):

The content of heavy metals As, Cd, Hg and Pb in sediments are far less than

the prescribed limit values for hazardous waste;

32

Persistent organic pollutants were not determined because of several

preliminary analyses of this material indicate that none of them are close to

the limit values for hazardous waste.

The second part of the H13 classification relates to the levels of pollutants in the

standard leachate. Here all relevant parameters were determined for the following

groups (Likar et al., 2009):

The mass of the drying residue was 10 times below the value limit;

The value of pH is neutral;

The content of heavy metals As, Cu, Ba, Be, B, Zn, Cd, Co, Sn, Ni, Cr, Se,

Te, Ag, Pb, Tl, In, and Hg are far below the limit values;

Toxic anions (sulphides, fluorides, nitrites, cyanides) in the leachate are not

present;

Organic substances in the leachate are not present in increased concentration.

As a general observation it is pointed out that the dredged material is not hazardous

waste.

The assessment of dangerous properties of sediments from the basins of the

Port of Koper

In accordance with the decree on waste management, OG RS No. 103/11, the

sediment samples from all three basins have no signs of hazardous waste. All

measured values, both in solid samples and in the leachate are significantly lower

than the prescribed limits in the decree. The measured values of certain parameters in

solid samples (e.g. for arsenic, lead) are 100 times lower, for some organic

parameters (e.g. for PAHs, PCBs, BTX, phenols). In accordance with the decree on

waste, OG RS No. 103/11, the values of cadmium are 1000 times lower than the

prescribed limits. Furthermore, on the basis of the content of the discussed

parameters measured in the sediment samples, it shows that they are usually below

the quantification limit or slightly above it. Due to the low levels, it can be estimated

that the measured values are not an indication of excessive pollution in terms of these

33

parameters. The exception is the content of mineral oil and mercury in solid sediment

samples, which are one of the main indicators of pollution in the basins of the Port of

Koper. Especially the Basin 2 can be regarded as polluted in terms of these two

parameters. The levels of these two parameters were the highest in this basin (sample

B2S2D). This is also confirmed with the results of the measured mineral oil and

mercury levels in sediment samples at the selected reference point in Koper Bay,

where the content of mineral oil and mercury is lower by half or more (Justin et al.,

2014).

The remaining measured parameters in the sediments of Koper Bay (with the

exception of iron and molybdenum in one sediment leachate sample) are located

within the ranges of results from the basins, meaning they are not the lowest. This

can mean that the sediments from the basins is not excessively polluted with other

discussed parameters due to anthropogenic activities, and that the chosen location of

Koper Bay can be regarded as a directed reference location of sediments to determine

the level of contamination (Justin et al., 2014).

Leaching tests (see Annex 4) were performed in accordance with BS EN

16192:2012. Sample preparation was carried out according to standard BS EN

15002: 2006.

34

3.3.2 Potential use of marine sediments for the production of clay bricks

Different analyses were conducted in order to determine if the marine sediments

containing larger quantities of clay are suitable for brick production.

The suitability of raw material for the production of clay products is tested in terms

of:

- the clay content,

- the content of free flint and carbonates,

- the size of particles (see Winkler’s diagram in Annex 2),

- the moisture content of the wet mass in the shaping process (plasticity),

- the shrinkage in the drying process, and

- the properties after firing.

In the lab, in accordance with practices in the brick industry, the following processes

and tests were carried out:

Testing of raw materials – marine sediments, which includes chemical analysis,

mineralogical analysis, particle size analysis, chloride and sulfate content

analysis;

Ceramic-technological testing process, which involved:

- Preparing the material on a vacuum extruder;

- Analyzing the firing process in a gradient furnace (to determine the klinker and

sinter points);

- Firing at selected temperatures;

- Determining the linear shrinkage, water absorption, compressive and flexural

strengths of experimental samples fired at selected temperatures.

35

3.4 Methods of analyses

3.4.1 Chemical analysis

The chemical composition was determined following the BS EN 196-2 method using

the X-ray fluorescence spectrometry (WD XRF).The results are given in 4.1.

3.4.2 Mineralogical analysis

The composition of the minerals in the samples was determined using the Philips

Norelco equipment for X-ray diffraction analysis by means of CuKα radiation

analysis obtained with a nickel filter. The recording rate was 10/min. The results are

given in 4.2.

3.4.3 Particle size analysis

The sample was washed through a 0.063mm sieve and the residual part was dried

and sieved again. The particles under 0.063mm were determined by the

sedimentation method according to the standard procedure BS-TS CEN ISO/TS

17892-4. This standard describes a method for determining grain composition of soil

samples. The grain structure is one of the most important physical characteristics of

the soil. The classification of soils is based mainly on the grain composition.

Granulation composition provides a description of the soil, based on the division into

separate classes according to the particle size. The size of each class can be

determined by sieving and/or sedimentation.

The humidity of the sample was determined according to the standard procedure BS-

TS CEN ISO/TS 17892-1 by drying samples at a temperature of T=40oC. The

procedure for determining the water content of a soil is to determine the mass of

water removed by drying the moist soil (test sample) to a constant mass in a drying

oven controlled at a given temperature, and to use this value as the mass of water in

the test sample related to the mass of solid particles. The soil mass that remains after

drying is used as the mass of the solid particles. The results are given in 4.3.

36

3.4.4 The sulfate content, water-soluble and total chloride

The chloride content as Cl- was determined by the BS EN 196-2:2013 method, where

the samples for the determination of soluble chloride were soaked for 24 hours in

distilled water. The samples for the determination of the total chlorides were

dissolved in nitric acid. Silver nitrate was added to both solutions and was titrated

with ammonium thiocyanate. The sulfate content was determined gravimetrically

according to the BS EN 196-2:2013 procedure, where the sample was dissolved in

hydrochloric acid and the sulfates precipitate with a solution of BaCl2.The results are

given in 4.4.

3.4.5 Ceramic-technological tests of clay

3.4.5.1 Determination of clay plasticity

Plasticity was determined according to the number of Pfefferkorn 3.33. So much

water was added to the mass that the sample cylinder of the initial height of 40mm

measured 12 mm after the deformation. The results are given in 4.5.1.

3.4.5.2 Firing in a gradient furnace

The samples were prepared using a vacuum (de-airing) extruder for making tiles with

measures of 50x20x8mm. The results are given in 4.5.2.

3.4.5.3 Firing process at three selected temperatures (950°C, 1050°C and 1100°C)

In this process, the sediments from Basin 1– surface area (s.1 in s.2), Basin 1 – depth

(s.1 in s.2), Basin 3 – surface area (s.1 in s.2), and Basin 3 – depth (s.1 in s.2) were

used. Eight kilograms of material was dried and homogeneously mixed. The samples

from the Basin 2 were excluded due to pollution (Basin 2 is more polluted because

there is an impact of the Rižana River that can be polluted by external influences,

like factory, septic tank collected in river, agriculture etc.), the samples from Koper

Bay were also excluded because not dredged. Test samples were shaped using a

laboratory de-airing extruder at a vacuum (see Figure 8). The following shapes were

obtained: cylinders, prisms and tiles. Test samples were dried for 7 days at ambient

37

room conditions, followed by 24h at 60°C and 8h at 100°C in a dryer. Dried samples

were then fired using heating rates of 100°/h up to 950°C or 1100°C with the holding

time at maximum temperature of 2h. The samples were then cooled in the furnace.

Figure 8: Forming the samples.

The following figures show the samples fired at 950°C (Figure 9), 1050°C (Figure

10) and 1100°C (Figure 11).

Figure 9: Samples fired at 950°C.

38

Figure 10: Samples fired at 1050 °C.

Figure 11: Samples fired at 1100 °C.

The analysis of the firing process in a gradient furnace provides information about

linear shrinkage and water absorption as a function of the firing temperature and

shows how likely it is for the clay to deform within a specific range of firing

temperatures. The results are given in 4.5.3.

3.4.5.4 The assessment of resistance to freezing

Testing the resistance to freezing of the bricks samples produced was carried out

following the BS EN 539-2:2013 method. The water absorption test was carried out

by submerging the brick product under water by 1/4 of its length per hour until fully

submerged, afterwards holding for 24 hours. As required by standard freeze-thaw

resistance was assessed visually (for example it there are cracks, crazes, spalling, loss

of materials). Five samples were tested and there were 50 cycles. The results are

given in 4.5.4.

39

3.4.6 Ceramic-technological testing of a mixture containing 40% of component A

and 60% component B

In the primary research, it was discovered that the sediments from Port of Koper are

only conditionally suitable raw material, so we started a new study and also a pilot

production in cooperation with Gorica brickworks. Due to financial constraints, we

decided to use one combination only. Already in lab tests, it was found that marine

sediments alone, without additives, are not suitable for direct brick production

(neither for pilot testing) because they, in the consistency suitable for shaping,

contain too much water, which affects the drying process (too high shrinkages).

Therefore, it was decided to prepare a mixture in cooperation with Gorica

brickworks. Based on many years of professional experience, a mixture was prepared

which provided appropriate parameters (plasticity, moisture content, allowed

shrinkages when drying) for industrial shaping. The mixture contained 40% of

component A and 60% of component B. The component B is not specified because it

is classified secret and the component A is marine sediments from Port of Koper. In

the end, the results of the samples from the pilot production showed the decision was

correct and the mixture appropriate.

For the purposes of the study and testing, the marine sediments from the port of

Koper were sent to Gorica brickworks in order to test if the sediments are an

appropriate addition to the basic raw material used for the production of brick blocks.

A mixture of 60% component B and 40% marine sediments was industrially

homogenized and used to shape blocks, which were fired and tested in the laboratory

and in regular production.

3.4.6.1 Chemical analysis

The chemical composition was determined following the BS EN 196-2 method using

the X-ray fluorescence spectrometry (WD XRF) of the ARL 8480S producer. See

results in 4.6.1.

40

3.4.6.2 Mineralogical analysis

The mineral composition was determined using an X-ray diffraction with the

Empyrean, PANalytical, X-ray powder diffractometer. The analysis was carried out

at a voltage of 45kV and a current of 40mA, with a CuKα anode, in an angular range

of 4–70° (2θ), with a step of 0.0131° 2ϑ.

An analysis of an average sample was carried out first. Then, clay fraction was

removed by centrifugation and directly recorded in the area of the main reflections.

To determine the possible presence of montmorillonite, clay fraction was exposed to

vapors of ethylene glycol for eight hours and then rerecorded. See results in 4.6.2.

3.4.6.3 The content of sulfates, chlorides and total salts

The mixture was also tested for the content of sulfates, and water-soluble and total

chlorides. The chloride content was determined by the BS EN 196-2:2013 method.

The samples for determining water-soluble chlorides were soaked for 24 hours in

distilled water, while the samples for determining total chlorides were dissolved in

nitric acid. Silver nitrate was added to both solutions and titrated with ammonium

thiocyanate. The sulfate content was determined gravimetrically according to the BS

EN 196-2:2013 method, where the sample was dissolved in hydrochloric acid and the

sulfates were precipitated with a solution of BaCl2. The results are given in 4.6.3.

3.4.6.4 Ceramic-technological tests of clay

Clay plasticity was determined according to the number of Pfefferkorn 3.33. by

adding so much water to the mass that the cylinder’s initial height of 40mm

decreased to 12mm after the deformation. See results in 4.6.4.

3.4.6.5 Results of firing in a gradient furnace

Before firing the samples in a gradient furnace, the samples were prepared by

pressing the mixture into 50x20x8mm tiles using a vacuum press. See results after

firing in a gradient furnace in 4.6.5.

41

3.4.6.6 Preparing and testing the mixture

First we homogenized the material. The samples - prisms, cylinders and tiles - were

shaped using a lab de - airing extruder vacuum press. The samples were first air dried

for a week, then dried for 24 hours at 60oC and afterwards for another 8 hours at

100oC in a dryer. Dried samples were then fired using heating rates of 100°/h up to

950°C or 1100°C with the holding time at the max temperature for 2 hours. Then, the

samples were cooled in the furnace. The results are given in 4.6.6.

Figure 12 shows the shaping and drying processes.

Figure 12: Shaping and drying the samples.

42

Figure 13 shows the appearance of the samples fired at 950°C.

Figure 13: Samples fired at 950 oC.

3.4.6.7 The assessment of the resistance to freezing

The samples fired at different temperatures were tested for their resistance to

freezing following the BS EN 539-2/2013 method. The water absorption test was

carried out by submerging the brick product under water by 1/4 of its length per hour

until fully submerged, afterwards holding for 24 hours. There were 50 cycles and 5

samples. See results in 4.6.7.

3.4.7 Testing modular blocks from pilot production

3.4.7.1 Determining sizes, BSEN 772-16:2011

At this stage, ten samples from pilot production were tested to determine their sizes.

The results are given in 4.7.1.

3.4.7.2 Determining the net volume and proportion of holes in bricks by weighing in

water, BS EN 772-3: 1999

To determine the net volume and proportion of holes in bricks, ten samples were

weighed in water. The results are given in 4.7.2.

43

3.4.7.3 Determining water absorption

Water absorption tests are based on measurements of dimensions according to BS

EN 772-03: 1999 and the determination of masses of dry and saturated samples

according to BS EN 772-13: 2002.The results are given in 4.7.3.

3.4.7.4 Determining holes and net volume, as well as the percentage proportion of

holes in clay and lime bricks filled with sand, BS EN 772-9:1999/A1:2005

For this purpose, ten samples were analyzed. See results in 4.7.4.

3.4.7.5 Determining net and gross density of dry bricks, BS EN 772-13:2002

Determination of net and gross density was made on 10 sample dry bricks. The

results are given in 4.7.5.

3.4.7.6 Determining compressive strength, BS EN 772 - 1:2011

a) Direction of loading:

No. of samples: 10 samples

Method of sample preparation: Grinding (7.2.4 of BS EN 772-1:2011)

Drying: 24 hours drying at 105°C, at least 4 hours

drying at room

Temperature (7.3.2b of BS EN 772-1: 2011)

Direction of loading: vertical (top and bottom surfaces)

44

b) Direction of loading:

No. of samples: 10 samples

Method of sample preparation: Grinding (7.2.4)

Drying: 24 hours drying at 105°C, at least 4 hours

drying at room

Temperature (7.3.2b of BS EN 772-1: 2011)

Direction of loading: Horizontal (side surfaces)

The results are given in 4.7.6.

3.4.8 Life Cycle Assessment – LCA

Primary data used were obtained from Gorica brickworks (the production company)

and Slovenian National Building and Civil Engineering Institute, which carried out

the chemical and physical analyses of the final product – a modular brick MB 29-19

(see Table 6). Furthermore, the data of the energy used in the production phase of the

product have been obtained from the analyses at the Gorica brickworks.

Table 6: Data used in the LCA for manufacturing 1 brick.

Part, item mass (kg)

Component A(Marine

sediments) *

Component B *

Modular brick 8,3

* data are classified and in a custody by the author as well as the Gorica brickworks.

Other data needed for the LCA study, such as transport paths, extraction of raw

materials, were obtained from direct measurements or with several databases, e.g.

45

ViaMichelin Route Planner (ViaMichelin, 2016) for calculating transport paths,

Econivent v2.1 for extraction of materials and energy production.

In the study, several assumptions have been made:

Production process: the marine sediments are acquired from the Port of Koper

and transported to Nova Gorica; due the fact that Ecoinvent v2.1 does not

include marine sediments as such neither any other processes for raw

materials, such as SiO2, Fe2O3 (which are the most representative components

in the marine sediments in our case) the following processes have been

assumed for production of the brick: CH: calcareon marl and RER:

aluminium oxide.

Construction and use: the material produces is transported from Nova Gorica

to Koper, where it is used for construction purposes; it was proposed that for

building a house 70 % of modular bricks are used and 30 % of wood (wooden

products have not been taken into consideration within our study) and that for

a 1sqm 16.6 bricks are needed.

End-of-life: Brick can be recycled in many ways. Scrap brick and brick from

demolition can be crushed and recycled into a new brick or used as brick

chips for landscaping, baseball diamonds and tennis courts. A recycled brick

can also be used as sub-base material for pavements, on quarry roads or even

as aggregate for concrete. Green building programs encourage the recycling

of construction waste and minimization of total waste generated (Brick

Industry Association, 2015). Thus is this study, it has been proposed to carry

out recycling processes. It has been assumed that the recycling process is

carried out in Nova Gorica, where the Centre for the reception and processing

of the non-hazardous construction waste is located. The recycling rate of the

construction waste in Slovenia is rather low, around 30% (ZAG, 2016),

which has been taken into consideration in the study as well as that the

recycling process savesabout40% of energy.

The environmental impacts have been calculated following the CML2001 impact

assessment method (Guinée 2001 a, b; Frischknecht et al., 2007), presenting a

method that restricts quantitative modeling to early stages in the cause-effect chain to

limit uncertainties (see Annex 3). See the results of LCA in 4.9.

46

4 RESULTS AND DISCUSSION

4.1 Chemical analysis

The results of the chemical analysis are given below.

Table 7: Chemical composition of the marine sediments - Basin 1

Sample Basin 1 –

surface area

(s.1)

Basin 1 –

surface area

(s.2)

Basin 1-

depth (s.1)

Basin 1-

depth (s.2)

Component Mass

fraction (%)

Mass fraction

(%)

Mass fraction

(%)

Mass fraction

(%)

Loss of ignition

(at 950 oC)

15.22 15.85 14.92 15.55

SiO2 46.45 47.72 46.58 47.96

Al2O3 12.68 12.21 13.32 12.26

Fe2O3 5.25 4.71 5.23 4.62

CaO 10.86 10.86 10.35 11.03

MgO 2.30 2.31 2.35 2.41

Na2O 1.79 1.71 1.70 1.59

K2O 2.09 1.87 2.38 1.97

TiO2 0.57 0.56 0.59 0.57

Table 7 shows the results for the Basin 1. It can be observed that SiO2 is the

predominant component, followed by Al2O3, CaO, Fe2O3, MgO, K2O, Na2O, and

TiO2.

47


Sample Basin 2 –

surface area

(s.1)

Basin 2 –

surface area

(s.2)

Basin 2-

depth (s.1)

Basin 2-

depth (s.2)

Component Mass

fraction (%)

Mass fraction

(%)

Mass fraction

(%)

Mass fraction

(%)

Loss of ignition

(at 950oC)

16.95 18.44 17.19 16.72

SiO2 50.47 46.57 46.56 46.14

Al2O3 10.43 11.60 11.39 12.57

Fe2O3 3.86 4.21 4.16 4.72

CaO 10.65 10.78 11.88 10.67

MgO 1.94 2.20 2.03 2.56

Na2O 1.84 2.01 1.86 1.88

K2O 1.25 1.36 1.45 1.95

TiO2 0.53 0.54 0.54 0.57

Table 8 shows that in the Basin 2 SiO2 is the predominant component, followed by

CaO, Al2O3, Fe2O3, MgO, Na2O, K2O, and TiO2.

48


Sample Basin 3 –

surface area

(s.1)

Basin 3 –

surface area

(s.2)

Basin 3-

depth (s.1)

Basin 3-

depth (s.2)

Component Mass fraction

(%)

Mass fraction

(%)

Mass fraction

(%)

Mass fraction

(%)

Loss of ignition

(at 950oC)

16.59 17.52 16.02 17.59

SiO2 45.62 45.53 46.18 45.11

Al2O3 12.29 12.27 12.67 12.26

Fe2O3 4.86 4.76 4.94 4.68

CaO 10.69 10.54 10.28 11.18

MgO 2.87 2.72 2.93 2.80

Na2O 1.74 1.97 1.80 1.99

K2O 2.03 1.89 2.17 1.85

TiO2 0.56 0.56 0.57 0.55

Table 9 shows that in the Basin 3 the SiO2 is the predominant component, followed

by Al2O3, CaO, Fe2O3, MgO, K2O, Na2O, and TiO2.

Table 10: Chemical composition of the marine sediments - Bay of Koper

Sample Bay of Koper surface area Bay of Koper depth

Component Mass fraction (%) Mass fraction (%)

Loss of ignition (at 950oC) 20.45 19.08

SiO2 41.77 42.33

Al2O3 11.14 11.27

Fe2O3 3.94 4.05

CaO 14.03 14.66 (continues on the

next page)

49

MgO 2.82 2.70

Na2O 2.01 1.68

K2O 1.27 1.50

TiO2 0.47 0.48

Table 10 shows that Koper Bay has SiO2 as a predominant component, followed by

Al2O3, CaO, Fe2O3, MgO, K2O, Na2O, and TiO2.

The chemical analysis indicates minor variations between individual basins as well

as between samples taken at the surface and at depth of the sea. These minor

variations are expected for natural raw materials. There are slightly larger variations

in composition when comparing the results of Koper Bay with the results from

individual basins. In the sample from Koper Bay, a lower SiO2 content and higher

carbonates content are noticeable. Furthermore, the results match well with the

results of X-ray analysis that also for the sample from Koper Bay shows a lower

content of SiO2 and a higher content of carbonates. Since the results of the sample

analyses are very similar, the mineralogical analysis were carried out only on the

samples of the Basin 1 and the samplesof Koper Bay.

50

4.2 Mineralogical analysis

The results of the mineralogical analysis are given below.

Table 11: The mineralogical composition of sediments

Sample Mineral composition Mass fraction %

Bay of Koper - depth

silica 7.4

chlorite,

illite/muscovite,

calcium montmorillonite,

60.9

feldspar, pyrite 3.2

calcite, dolomite 28.5

Basin 1 surface area, s .1

silica 19.8

chlorite,

illite/muscovite,

calcium montmorillonite

55.6



Basin 1 depth, s .1

silica 13.8

chlorite,

illite/muscovite,

calcium montmorillonite

63.1



The mineralogical composition of clays and sediments provides important

information in the process of identifying the raw material composition, because the

properties of clay and, in particular, the shaping, drying and firing processes depend

more on the minerals present in raw material than on the chemical composition of the

material. The content of clay particles in brick clay may vary from 20 to 60%, but it

51

usually amounts to 30%. Table 11 shows the clay examined contains about 55–63%

clay particles. The minerals in the clay belong to the chlorite-illite group.

“The chlorites are a group of phyllosilicate minerals. Chlorites can be described by

the following four end members based on their chemistry via substitution of the

following four elements in the silicate lattice; Mg, Fe, Ni, and Mn” (Chlorite group

2015).

Figures 14–19 show the mineralogical composition of the samples taken in the Basin

1 and Koper Bay.

Figure 14: Chromatogram “Basin 1 - surface – S1”.

Figure 15: Chromatogram “Basin 1 - surface - S1” – fraction <2 m.

52

Figure 16: Chromatogram “Basin 1 - depth - S1”.

Figure 17: Chromatogram “Basin 1 - depth- S1” – fraction <2 m.

Figure 18: Chromatogram “Bay of Koper - depth”.

53

Figure 19: Chromatogram “Bay of Koper - depth” - fraction<2 m.

Another important piece of information is the amount of quartz. In clays it is found

as fine sand and its content in brick clay is usually between 20% and 50%. This is

important as quartz affects the product properties as well as the drying process

(reduces the sensitivity) and the firing process, where during the cooling process it is

necessary to consider the phase transition of flint at 573oC, which is connected to

volume changes and may lead to cracking, if the cooling process is not properly

controlled. As the X-ray analysis of a sample shows, the clay tested contains about 7-

20% of quartz; comparing all samples taken, the samples from the Port of Koper

contain the lowest amounts of quartz but considerably higher amounts of calcite and

dolomite.

If carbonates are finely dispersed, their content may reach as much as 20-25%, but a

problem may arise with lime inclusions larger than 1 mm. There is no sign of lime

inclusions larger than 1 mm in the clay examined; the carbonate content ranges from

15–19% in the Basin I to about 29% in Koper Bay. If lime inclusion (as free lime -

CaO) are bigger than 1 mm in the clay body and it they are near the surface of the

brick unit, white burst or pop-outs can be formed as the free lime hydrates and

becomes calcium hydroxide [Ca(OH)2]. This reaction results in a volume increase.

Exposure to air, and consequently to carbon dioxide in the air, further forms calcium

carbonate (CaCO3). If the quantity is not very high, this does not impair the product

quality but may be bothering from the aesthetic point of view.

54

4.3 A particle size analysis

Table 12 shows the particle size distribution and the moisture content of the samples

taken in the Basin 1 and Koper Bay.

Table 12: The particle size distribution and the moisture content

Sample Particle size Moisture

content

% <20 m % >20 m % <63 m %

Basin 1 – surface area

–s.1

81 19 90 78

Basin 1 – depth – s.1 89 11 97 86

Bay of Koper – depth 80 20 93 77

The figures below shows the particle size distribution of samples taken in the Basin 1

at the surface (Figure 20) and at depth (Figure 21), and Koper Bay (Figure 22).

Figure 20: The particle size distribution of the sample “Basin 1 - surface - S1”.

55

Figure 21: The particle size distribution of the sample “Basin 1 - depth - S1”.

Figure 22: The particle size distribution of the sample “Bay of Koper - depth”.

The particle size distribution in the raw material also has a significant effect on the

properties of clay during the shaping, drying and firing processes as well as on the

properties of dry and fired products. The use of the clay can be partially defined on

the basis of its granulation, which is shown by the Winkler’s diagram for brick

products (Annex 2). Annex 2 clearly shows that the examined clay has a very large

proportion of fine particles but still lies within the range suitable for production of

hollow brick products.

56

4.4 The sulfate content, water-soluble and total chloride

The results of the analysis of the sulfate content, water-soluble and total chloride are

given in Table 13.

Table 13: The sulfate content, water-soluble and total chloride

Sample The content of

sulfate (%)

The content of

water-soluble

chloride (%)

The content of

total chloride (%)

Composite /dried 0.43 1.676 1.676

Composite/ fired

at 950oC

/ 0.60 0.65

Composite/ fired

at 1050oC

/ 0.036 0.0045

The data quantified the chloride content and, as expected, it is 1.7% in a non-

fired/wet state. For this reason, the impact of chlorides on corrosion needs to be

evaluated as well. The chloride content drops after firing, chloride content are almost

negligible at temperature above 1050oC; their amount is only 0.036 %(as a

comparison, the limit for chlorides in cements is 0.1% according to BS EN 196-1).

Water-soluble chlorides are still present (0.6 %) when firing at a lower temperature

(950oC), and they may be washed out in the environment following exposure to

normal climate conditions.

57

4.5 Ceramic-technological tests of clay

4.5.1 Determination of clay plasticity

The results of the analysis of clay plasticity are given in Table 14.

Table 14: Plasticity determination

Sample M dry

(g)

M wet

(g)

Moisture

based on dry

mass (%)

Moisture

based on wet

mass (%)

Basin 1 - surface area -s.1 40.17 56.47 40.6 28.9

Basin 1 – depth –s.1 40.86 57.41 40.5 28.8

Bay of Koper - depth 42.31 60.02 41.9 29.5

Table 15: Plasticity classification

Plasticity Very low Low Medium High Very

high

Moisture based

on dry mass (%)

16 20 25 30 40

Moisture based

on wet mass (%)

13.8 16.7 20 23.1 28.6

According to plasticity classification (see Table 15), the sediments analyzed belong

to very high plasticity clay.

The plasticity of clay is important from several aspects. If the raw material is not

plastic enough, it is hard to shape it, and dry products are fragile and may get

damaged during ordinary transport. However, if the clay is too plastic, it dries very

slowly and retains moisture in the interior, which can lead to cracking and bending.

High moisture content of wet mass is not desirable because more energy is needed in

the drying process in order to remove all moisture. The moisture content of wet brick

clay is usually between 17% and 25%; it amounts to about 29% in the clay

examined.

58

4.5.2 Results of firing in a gradient furnace

Results of shrinkage and absorption analyses are presented in Table 16.

Table 16: The shrinkage and water absorption depending on the firing temperature

Temperature (°C) Shrinkage (%) Absorption (%)

785 0.5 23.7

829 -0.1 24.0

876 -0.6 24.6

918 -0.6 24.5

967 0.1 24.6

1020 -0.1 25.7

1065 0.6 23.0

1114 7.6 5.4

1152 11.0 0.9

Tklinker: 1112oC

Tsinter: 1137oC

The graph of the shrinkage and water absorption of temperature firing is shown in

Figure 23, and the appearance of the samples after the firing is shown in Figure 24.

Figure 23: The graph shows the shrinkage and water absorption depending on firing temperatures.

59

Figure 24: The appearance of samples after firing in a gradient furnace.

4.5.3 Firing process at three selected temperatures (950°C, 1050°C and 1100°C)

The results of firing in a gradient furnace suggested that the examined clay is a

highly sensitive type of raw material because it “closes” very fast at temperatures

higher than 1070°C. This means that as the firing temperature rises, the water

absorption quickly lowers while the shrinkage increases. When firing at about

1150°C, clay is vitrified because the water absorption falls below 1%. The clinker

point (water absorption 6%) is at 1112°C while the sintering point (water absorption

2%) is at 1143°C.Table 17 on the next page shows the conditions of shaping the

specimens and the characteristics of clay.

The final properties of dried and fired products, which are shown in the table above,

deviate from the expected values for typical brick clay. During drying, shrinkage is

very high, about 12% (depending on the orientation when shaping). When designing

a tool for shaping products, the overall shrinkage during drying and firing has to be

considered. The products fired at 950oC and 1050

oC have a high absorbency rate,

while when fired at 1100oC, the water absorption drops to 7%, but these samples

60

tend to bend and inflate. The values of compressive and flexural strength are high.

The material is also resistant to freezing when fired at 1100°C but non-resistant to

freezing when fired at 950oC and 1050

oC.

Table 17: The conditions of shaping the samples and the characteristics of clay after firing and drying

DESCRIPTION OF THE SAMPLE Composite

FORMING

Vacuum 0.82-0.85

3.08

41.0

29.1

No. after Pfefferkorn

% moisture based on dry mass

% moisture based on wet mass

SHRINKAGE WITH DRYING (%)

measured along the prism length 12.0 12.0 12.4

measured across the prism width 11.8 12.0 11.9

FIRING AT TEMPERATURE 950

±10°C

1050

±10°C

1100

±10°C

SHRINKAGE AFTER FIRING (%)

measured along the prism length 0.5 0.7 6.4

measured across the prism width 0.4 1.0 9.2

WATER ABSORPTION (%) 23.1 22.6 7.0

prism

LOSS OF MASS (%) 15.5 17.4 15.8

prism

BENDING STRENGHT (MPa) 3.2 8.7 19.3

prism

DENSITY (g/cm3) 1.5 1.6 2.0

prism

COMPRESSIVE STRENGHT (MPa) 25.7 36.4 96.8

cylinder

61

On the basis of primary analyses and samples prepared in a lab, it was established

that the marine sediments without any additives are only conditionally suitable as

source material for producing clay products. The major problem arises with too high

drying shrinkage, which amounts to about 12%, while the usual shrinkage with brick

clay is below 3–4%. In order to ensure water absorption below 20% (which is normal

for protected/plastered bricks) or below 6% (which is normal for bricks directly

exposed to weather conditions), the firing process has to be carried out at high

temperatures and within a limited temperature range, which is quite difficult to

provide under industrial conditions.

4.5.4 The assessment of the resistance to freezing

The results are given in Table 18.

Table 18: The assessment of resistance to freezing

Sample label Water absorption Damage description

masss (g) massm (g) W (%)

950oC -1 98.06 121.15 23.5 The surface is damaged










1100oC -1 94.90 98.78 4.1 No damages

1100oC -2 96.12 99.88 3.9 No damages

1100oC -3 96.37 99.03 2.8 No damages

1100oC -4 96.84 101.14 4.4 No damages

1100oC -5 100.10 103.59 3.5 No damages

Mass s – dry mass in g (dried at 110oC)

Mass m – wet mass in g (after soaking in water for 24 hours)

62

The appearance of the samples after testing the resistance to freezing is shown in

Figures 25, 26 and 27(the circles and holes were present before the testing).

Figure 25: The appearance of the samples fired at 950oC after testing the resistance to freezing.



63

The sediments from the port of Koper contain large amounts of water (more than

70%) and therefore have to be dried beforehand. For this reason it is best to find a

dry additive because this will facilitate the regulation of water content needed in the

shaping process (now the water content is about 29%).

To improve the process and to achieve optimal properties in the technological

process of shaping ceramic products, further investigations have to be carried out

using possible additions, which reduce plasticity and the drying shrinkage.

64

4.6 Ceramic-technological testing of a mixture containing 40% of component A

and 60% of component B

4.6.1 Chemical analysis

The results are shown in Table 19.

Table 19: Chemical composition of the mixture

Component Mass fraction (%)

Loss of ignition (at 950oC) 10.76

SiO2 52.50

Al2O3 13.74

Fe2O3 5.69

CaO 7.49

MgO 2.24

Na2O /

K2O 2.56

TiO2 0.69

4.6.2 Mineralogical analysis

The results are given in Figures 28 and 29.

Figure 28: Diffractogram of an average unfired sample.

65

Figure 29: Diffractogram of an unfired mixture - fraction below 2 m.

Table 20 shows the proportion of silica and clay fraction.

Table 20: Mineral composition of the sample

Mineral composition Proportion by weight %

Silica 32

Illite/muscovite

Chlorite

Ca montmorillonite

37

Feldspar

Calcite

Dolomite

66

4.6.3 The content of sulfates, chlorides and total salts


Table 21:The content of sulfates, chlorides and total chlorides

Sample The content

of acid-

soluble

sulfate (%)

The content

of water-

soluble

sulfate (%)

The content

of total

chloride

(%)

The content

of water-

soluble salts

(%)

Unfired mixture 0.64 0.274 0.54 0.94

Fired brick

(P 157/16-480-1)

0.24 0.035 0.11 0.66

4.6.4 Ceramic-technological tests of clay

The results of the ceramic-technological tests are given in Table 22. The

classification of clays in terms of plasticity is given in Table 23.

Table 22: Determining plasticity

Sample M dry (g) M wet (g) Moisture

based on dry

mass (%)

Moisture based on

wet mass (%)

Unfired mixture 52.11 66.92 28.4 22.1

Table 23: Plasticity classification

Plasticity Very low Low Medium High Very high

Moisture based

on dry mass (%)

16 20 25 30 40

Moisture based

on wet mass (%)

13,8 16,7 20 23.1 28,6

67

In terms of plasticity classification, the marine sediments analyzed belong to very

high plasticity clay.

4.6.5 Results of firing in a gradient furnace

The results are presented with a table (Table 24) and a graph (Figure 30).

Table 24: The shrinkage and water absorption depending on the firing temperature

Temperature (°C) Shrinkage(%) Water absorption (%)

784 -0.1 16.4

838 0.2 14.9

889 0.6 13.9

933 0.8 13.8

983 0.8 13.9

1040 0.9 13.7

1090 1.8 10.5

1134 5.1 0.7

1178 / /

Tklinker: 1110oC

Tsinter: 1128oC

The graph showing the shrinkage and water absorption depending on firing

temperatures is shown in Figure 30, while the appearance of samples after firing is

seen in Figure 31.

68

Figure 30: The graph showing the shrinkage and water absorption depending on firing temperatures.

Figure 31: The appearance of the samples after firing in a gradient furnace.

69

4.6.6 Preparing and testing the mixture

Table 25 shows the conditions of shaping the samples and the characteristics of clay

after firing and drying.

Table 25: The conditions of shaping the samples and the characteristics of clay after firing and drying

DESCRIPTION OF THE SAMPLE Mixture

(40% component A, 60% component B)

SHAPING

Vacuum 0.82-0.85 kg/cm2

1.7

23.6

19.1

No. after Pfefferkorn

% moisture based on dry mass

% moisture based on wet mass

SHRINKAGE AFTER DRYING (%)

measured along the prism length 7.9

measured across the prism width 6.2

FIRING AT TEMPERATURE 950 ± 15O

C

SHRINKAGE AFTER FIRING (%)

measured along the prism length -0.3

measured across the prism width -0.1

WATER ABSORPTION (%)

prism 13.4

MASS LOSS (%)

prism

10.5

FLEXURAL STRENGTH (MPa) 6.9

prism

DENSITY (g/cm3) 1.79

prism

COMPRESSIVE STRENGTH (MPa) 87.7

70

4.6.7 The assessment of the resistance to freezing

Table 26 shows the results after freezing.

Table 26: The results after determining the resistance to freezing.

Sample label W (%) Damage description

950oC -1 15.6 The surface is damaged









1100oC -1 5.7 No damage





71

Figure 32 shows the appearance of the samples after freezing.

Figure 32: The appearance of samples fired at 950, 1050 and 1100 oC after freezing.

72

The chemical analysis of the mixture shows that, in comparison to marine sediments

alone, the mixture has a lower loss of ignition, which is in part a result of a lower

content of carbonates (lower CaO content). The mixture also contains more SiO2than

the marine sediment alone.The plasticity of the mixture is lower than the plasticity of

marine sediment. The mixture belongs to medium to high plasticity clay.

The normal moisture content of wet clay mass is 17–25%; the moisture content of

the mixture is 19.1% and of the marine sediment alone is about 29%, meaning that

the mixture is more appropriate for shaping than the marine sediment alone.

An analysis of firing in a gradient furnace gives information about the linear

shrinkage and water absorption in dependence of firing temperatures and tells how

susceptible clay to deformation within a specified firing temperature range is. The

results of firing in a gradient furnace show that the mixture analyzed is highly

susceptible as it “closes” at temperatures higher than 1090oC, which means that the

water absorption decreases and shrinkages increase quickly at higher temperatures.

When firing at about 1130oC, the clay is actually glazed as the water absorption

decreases below 1%, and the firing at 1180oC even causes clay samples to blow up.

The klinker point (water absorption 6%) is at 1110oC and the sinter point (water

absorption 2%) is at 1128oC, which is an extremely narrow interval.

After drying and firing, the shrinkage of the mixture is 6.2–7.9% (depending on the

direction of the forming process), which is almost half the shrinkage of the marine

sediment alone. After firing at 950oC, the shrinkage of the mixture is about -0.2 %,

while the shrinkage of the sediment alone is about 0.5%. The water absorption of the

mixture is 13.4% and about 23.1% of the marine sediment.

The mixture of components A and B shows significantly higher compressive and

flexural strengths than the sediments alone; the flexural strength of fired sediments

samples is 3.2MPa, and 6.9MPa of the mixture samples, while the compressive

strength of the fired sediment samples is 25.7MPa, and 87.7MPa of the mixture.

On the basis of the analyses performed, it can be concluded that the mixture of

component B and marine sediments is a more appropriate raw material for producing

73

bricks. This is because the marine sediments alone have very high shrinkage, about

12%, during the drying process, while the shrinkage of the mixture is between 6.2%

and 7.9%, which is still higher than with the common brick clay, where the shrinkage

is below 3–4% (some differences are a consequence of high vacuum in the shaping

process of clay on industrial extruders). Furthermore, the mixture samples have a

lower rate of water absorption and significantly higher mechanical properties.

The mixture shows resistance to freezing after firing at 1100oC, while it is not

resistant to freezing after firing at 950oC and 1050

oC, which is similar to firing the

marine sediment alone.

In collaboration with Gorica brickworks, a pilot production was started where bricks

composed of 40%component A and 60% component B were made, which should

have the same characteristics as conventional bricks - modular brick.

4.7 Testing modular blocks from pilot production

4.7.1 Determining sizes, BSEN 772-16:2011


Table 27: Determining sizes

Sample Length Width Height Wall thickness (mm)

number (mm) (mm) (mm) outer inner

1 189.2 290.8 186.5 10.5 6.7

2 188.5 290.2 186.6 10.7 6.5

3 188.9 290.8 186.3 10.7 6.5

4 188.7 290.2 185.9 10.5 6.5

5 188.9 291.0 186.4 10.8 6.5

6 188.5 290.5 186.7 10.6 6.5

7 189.0 290.5 185.7 10.5 6.8

8 189.0 291.0 186.9 11.1 6.4

9 188.5 290.0 186.4 10.8 6.5

10 189.1 291.0 186.6 10.2 6.6

Average 188.8 290.6 186.4 10.6 6.6

74

The average combined thickness of the inner and outer walls on the line:

- in length: 51.0 mm or 27% of the length

- in width: 57.0 mm or 20% of the width

4.7.2 Determining the net volume and proportion of holes in bricks by weighing in

water, BS EN 772-3: 1999


Table 28: Determining the volume and proportion of holes in brick by weighing in water

Sample Volume (104 mm

3) of Proportion

number solid part brick holes of holes (%)

1 411 1026 614 60

2 407 1020 613 60

3 409 1023 614 60

4 405 1017 612 60

5 409 1025 615 60

6 407 1022 615 60

7 405 1019 614 60

8 409 1028 618 60

9 407 1018 612 60

10 410 1027 616 60

Average 408 1022 614 60

Note: The proportion of holes is determined without deductions for mortar

pockets and indentations on the surface (point 5.2.2.5 of BS EN 771-1: 2004).

75

4.7.3 Determining water absorption

Results of water absorption tests are given in Table 29.

Table 29: Determining water absorption

Sample Weight Water absorption

number dry wet (%)

1 7642 8588 12.4

2 7571 8513 12.4

3 7604 8539 12.3

4 7525 8455 12.4

5 7604 8549 12.4

6 7567 8496 12.3

7 7517 8444 12.3

8 7609 8546 12.3

9 7548 8483 12.4

10 7602 8556 12.5

Average 12.4

St. dev. 0.1

76

4.7.4 Determining holes and net volume, as well as the percentage proportion of

holes in clay and lime bricks filled with sand, BS EN 772-9:1999/A1:2005

The results of determining the proportion of holes in bricks are given in Table 30.

Table 30: Determining holes and net volume

Sample Volume (mm3) x 10-4

of Proportion of

number brick holes (sand) holes (%)

1 1026 581 57

2 1020 588 58

3 1023 584 57

4 1017 583 57

5 1025 586 57

6 1022 588 58

7 1019 585 57

8 1028 585 57

9 1018 584 57

10 1027 582 57

Average 1022 585 57

77

4.7.5 Determining net and gross density of dry bricks, BS EN 772-13:2002

The results of determining net and gross density of 10 sample dry bricks are given in

Table 31.

Table 31: Determining net and gross density of dry bricks

Sample Density (kg/m3)

number gross net

1 745 1858.5

2 742 1858.8

3 745 1859.2

4 740 1856.2

5 740 1857.8

6 740 1857.8

7 740 1856.0

8 740 1859.0

9 741 1856.4

10 740 1853.7

Average 740 1857.3

78

4.7.6 Determining compressive strength, BS EN 772 - 1:2011

Table 32 shows the results in case of vertical loading.

Table 32: Determining compressive strength (height)

Sample Length Width Height after Breaking Compressive

number (mm) (mm) grinding (mm) strength (N) strength(MPa)

11 189 290 184 820000 15.0

12 189 291 184 1576000 28.7

13 189 290 185 1801000 32.9

14 189 290 185 1397000 25.5

15 189 291 184 1835000 33.4

16 189 291 184 1061000 19.3

17 188 290 184 1545000 28.3

18 189 290 184 1269000 23.1

19 188 290 184 1603000 29.4

20 189 290 185 1405000 25.7

Average 26.1

St. dev. 5.8

Variation coefficient: 22.2 %.

79

Table 33 shows the results in case of horizontal loading.

Table 33: Determining compressive strength (length)

Sample Height Width Breaking Compressive

number (mm) (mm) strength (N) strength (MPa)

1 187 291 445000 8.2

2 187 290 557000 10.3

3 186 291 526000 9.7

4 186 290 541000 10.0

5 186 291 535000 9.9

6 187 291 585000 10.8

7 186 290 528000 9.8

8 187 291 521000 9.6

9 186 290 460000 8.5

10 187 291 533000 9.8

Average 9.7

St. dev. 0.8

Variation coefficient: 8.2%.

80

4.8 Comparison of the regular production and pilot production

The blocks from the pilot production were made of a mixture of 60% of component

B and 40% of component A (marine sediments from the Port of Koper).

Table 34 provides a comparison of characteristics of the pilot production and

regular production (summarized from the report no. P 664/04-480-10 dated

22/01/2016 with the permission of the client).

Table 34: Comparison between a pilot production and regular production

Modular block MB 29-19

Characteristics

(average values)

Pilot

production

(P157/16-480-

1)

Regular

production

(P 664/04-

480-10)

Requirements

EN 771-1 and

Eurocode 8

Dimensions:

- length (mm)

- width (mm)

- height (mm)

- thickness of outer walls (mm)

- thickness of inner walls (mm)

189

291

186

10.6

6.6

189

291

186

10.9

7.2

Declared values

and deviations

Hollowness – method with sand

(%)

57 56 Max. 55% for

load-bearing

walls of

categories I and

II

Compressive strength:

- at top/bottom (MPa)

- at sides (MPa)

≥ 26.1

≥ 9.7

25.1

8.6

Min 10 MPa

Min 2.5 MPa

Water absorption (%) 12.4 12.0 /

Gross density (kg/m3)

Net density (kg/m3)

740

1857

795

1906

Declared values

and deviations

81

After comparing the results, it has been concluded that the samples from the pilot

production also meet the requirements of the standard EN 771-1:2011+A1:2015:

Specification for masonry units - Part 1: Clay masonry units and requirements of

Eurocode 8: Design of structures for earthquake resistance, 1998.

A greater variation between the results from the pilot production and the regular

production is seen in density; the samples with added marine sediments have a lower

density of the solid part (net density) and therefore also lower gross density (lower

gross density is in part also a result of thinner walls or greater hollowness).

Figure 33 shows a modular brick sample from the pilot production.

Figure 33: Pilot production: Brick – modular brick MB 29-19, 190 x 290 x 190 mm.

82

4.9 Results of Life Cycle Assessment – LCA

The LCA results in Figure34 indicate that the most significant impacts from the

system are global warming potential (GWP) and human toxicity potential (HTP),

followed by acidification potential (AP) and eutrophication potential (EP).

Figure 34: Environmental impacts of the MB 29-19 in its life cycle.

The above results obtained were further normalized. The normalization is a process,

which shows the scope of impact category, and its contribution to the overall

environmental impacts on a global or regional level. Thus, the goal of normalization

is usually two-fold:

To put the result in a wider context and

to adjust the results that share a common dimension.

The purpose of normalization is to better understand the relative importance and the

deviation of the results obtained. The normalization is performed in such a way that

the results obtained are compared to a reference situation, which means that the

deviation of the results obtained are converted according to the reference data for the

same reference area. The reference zone may be a single country or region. In this

study, a reference area of Europe 25+3 (Anneke et al., 2008) was chosen, where the

2,28E-06 4,22E-07

1,19E-03

2,99E-05

3,73E-12

2,07E-07 1,24E-07

1,00E-12

1,00E-09

1,00E-06

1,00E-03

AcidificationPotential (AP) [t

SO2-Equiv.]

EutrophicationPotential (EP) [t

Phosphate-Equiv.]

Global WarmingPotential (GWP 100years) [t CO2-Equiv.]

Human ToxicityPotential (HTP inf.)

[t DCB-Equiv.]

Ozone LayerDepletion Potential(ODP, steady state)

[t R11-Equiv.]

Photochem. OzoneCreation Potential(POCP) [t Ethene-

Equiv.]

TerrestricEcotoxicity Potential

(TETP inf.) [t DCB-Equiv.]

Impact categories

ton

s

83

eutrophication potential (EP) is the most dominant, followed by the global warming

potential (GWP) and the acidification potential (AP), see Figure 35.

Figure 35: Normalized environmental impacts (based on the Europe 25+3 normalization) of the MB

29-19 in its life cycle.

Figure 36: A relative contribution of different life cycle stages to the total environmental impacts.

A relative contribution (see Figure 36) shows that the most significant “hot spot” in

the life cycle is the production process. It is the largest contributor to all the impact

categories, especially ozone layer depletion potential (ODP) and terrestic eco-

8,03E-14

1,22E-12

2,29E-13

1,32E-14

5,49E-16

7,40E-15

1,94E-14

1,00E-16

1,00E-14

1,00E-12

1,00E-10


SO2-Eq./a]


Phosphate-Eq./a]

Global WarmingPotential (GWP 100years) [t CO2-Eq./a]


[t DCB-Eq./a]


[t R11-Eq./a]


Eq./a]

TerrestricEcotoxicity Potential(TETP inf.) [kg DCB-

Eq./a]

Impact categories

ton

nes

0%

20%

40%

60%

80%

100%


SO2-Equiv.]


Phosphate-Equiv.]

Global WarmingPotential (GWP 100

years) [t CO2-Equiv.]


[t DCB-Equiv.]


[t R11-Equiv.]


Equiv.]

TerrestricEcotoxicity

Potential (TETP inf.)[t DCB-Equiv.]

Production Use

End-of-life

Co

ntr

ibu

tio

n t

o

84

toxicity potential (TETP), while the construction and use phases, as well as the end-

of-life phase contributing less to the overall impacts.

Table 35 provides a list of selected emissions to the air from various life cycle stages.

The selection of these emissions is based on the substances referred in the ordinance

for the quality of the outdoor air and the Slovenian law for environmental protection.

As expected, over the whole life cycle, production phase contributes the most to the

emissions sulphur dioxide, nitrogen oxides, carbon dioxide, volatile organic

compounds and particulate matter.

Table 35: Emissions to the air (tons) for MB 29-19 in its life cycle

EMISSIONS PRODUCTION USE END-OF-LIFE

SO2 7.78 10-8

5.67 10-9

9.69 10-9

NOx 1.63 10-6

6.00 10-6

7.70 10-6

CO2 0.70 10-3

6.80 10-5

0.41 10-3

VOC 2.30 10-7

3.90 10-8

7.31 10-8

PM 1.44 10-5

1.57 10-8

1.85 10-8

85

5 CONCLUSIONS

It has been proved that the measured values of potential harmful substances in

marine sediments do not exceed the prescribed limits, in accordance with the

Regulation on waste, Official Gazette of RS, no. 103/11. All measured values, both

in solid samples and in the leachate, are even significantly lower than the prescribed

limits in the decree. The exception is the content of mineral oil and mercury in solid

sediment samples in the basins of the Port of Koper; especially the Basin 2 - the

levels of these two parameters were the highest in this basin (sample B2S2D). But if

such material is fired, the firing process usually causes immobilization of heavy

metals so that they no longer pose a potential threat to the environment, what was

also proved in our study by leaching tests. This has confirmed the first hypothesis

that marine sediments from the port of Koper are non-dangerous in terms of their

chemical composition and can be further used.

Different analyses were conducted to determine if the marine sediments containing

larger quantities of clay is suitable for brick production. On the basis of primary

analyses and samples prepared in a lab, it was established that the sediments without

any additives is only conditionally suitable as source material for brick production.

After initial analyses a new study and a pilot production were started in cooperation

with Gorica brickworks where 40% of component A (marine sediments) and 60% of

component B were mixed. The results of the chemical tests show that, in comparison

to the marine sediments alone, the mixture of marine sediments and component B

has a lower loss of ignition, which in part results from a lower carbonate content (a

lower CaO content), and a higher SiO2 content. Moreover, the mixture has a lower

plasticity than the marine sediments alone. The mixture belongs to middle-to high-

plasticity clay.

The usual moisture content based on wet mass of brick clay is between 17% and

25%. The moisture content of the mixture is 19.1%, while the moisture content of the

marine sediments is 29%, which means that the mixture of marine sediments and

component B is more appropriate for shaping than the sediments alone. These

86

conclusions have confirmed the second hypothesis that the marine sediments in

combination with other material can be due to chemical and mineralogical

compositions as well as due to the particle size used in construction sector, especially

for the for brick production.

The LCA study has shown that the most significant impacts of the modular brick

life-cycle are global warming potential (GWP) and human toxicity potential (HTP),

followed by acidification potential (AP) and eutrophication potential (EP). A

calculated relative contribution has shown that the production process is the largest

contributor to all the impact categories. This is expected, since production of the

modular brick is linked to the extraction of raw materials and production process,

which are both energy and material consuming. However, this presents an interesting

issue in terms of production processes and eco-design, such as a usage of the

materials that could be recycled, in order to reduce the environmental impacts in the

production phase. The LCA study has confirmed the third thesis that the products

(bricks) based on the marine sediments meet the requirements of sustainable

production from the perspective of LCA.

In this study, an alternative solution for using dredged sediments for the production

of bricks is proposed. The results of the research and pilot production show that

because of its perpetual availability, homogeneity and mineralogical, petrographic

and chemical composition, the marine sediments mixed with some additives are a

suitable raw material for brick production.

87

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93

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34/2008)

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57/2008)

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BS EN 771-1: 2011+A1:2015 Specification for masonry units - Part 1: Clay masonry

units.

BS EN 772-1:2011+A1:2015 Methods of test for masonry units. Determination of

compressive strength.

BS EN 196-2:2013 Methods of testing cement – Part 2: Chemical analysis.

BS EN 539-2:2013 Clay roofing tiles for discontinuous laying. Determination of

Physical characteristics. Test for frost resistance.

BS EN 933-1: 2012 Tests for geometrical properties of aggregates. Determination of

particle size distribution. Sieving method.

BS EN 772-16:2011 Methods of test for masonry units. Determination of

dimensions.

BS EN 772-1:2011 Methods of test for masonry units: Part 1 Determination of

compressive strength.

BS EN 772-3: 1999 Methods of test for masonry units - Part 3: Determination of net

volume and percentage of voids of clay masonry units by hydrostatic weighing.

BS EN 772-9:1999/A1:2005 Methods of test for masonry units – Part 9:

Determination of volume and percentage of voids and net volume of clay and

calcium silicate masonry units by sand filling.

BS EN 772-9:1999/A1: 2005 Methods of test for masonry units - Part 9:

Determination of volume and percentage of voids and net volume of calcium silicate

masonry units by sand filling.

BS EN 196-1: 2005 Methods of testing cement. Determination of strength.

BS EN 771-1: 2004 Specification for masonry units - Part 1: Clay masonry units.

94

BS-TS CEN ISO/TS 17892-4: 2004 Geotechnical investigation and testing -

Laboratory testing of soil -- Part 4: Determination of particle size distribution.

BS-TS CEN ISO/TS 17892-1 2004 Geotechnical investigation and testing -

Laboratory testing of soil -- Part 1: Determination of water content.

BS EN 772-13: 2002 Method of test for masonry units – Part 13: Determination of

net and gross dry density of masonry units (except for natural stone).

BS EN 196-2: 1995 Methods of testing cement. Chemical analysis of cement.

ISO 2006a. 14040 - Environmental Management - Life cycle assessment - Principles

and framework. Geneva. Switzerland.

ISO 2006b. 14044 - Environmental Management - Life cycle assessment -

Requirements and Guidelines. Geneva. Switzerland.

95

ANNEXES

ANNEX 1

The sediment sample 1, from the Basin 1, taken at a depth of 1m and surface 10cm.

The sediment sample 2 from Basin 1, taken at a depth of 1m and surface 10cm.

96

The sediment sample 1 from Basin 2, taken ata depth of 1m and surface 10cm.


97


The sediment sample 2 from Basin 3, taken ata depth of 1m and surface10cm.

The sediment sample 1 from Koper Bay, taken at a depth of 1m and surface10cm.

98

ANNEX 2

Placement of sediment in Winkler’s diagram

Tags: B-G – Basin 1 - depth

B-P – Basin 1 - surface area

K-Z – Bay of Koper - depth

99

ANNEX 3

CML 2001 is a method of assessing the impacts on the environment, which

represents a quantitative modeling from the initial to final states in causal

relationships and limits uncertainty. The results obtained with this method are

grouped into categories based on common mechanisms and calculated based on

reference material, for example SO2 is reference gas for acidification, CO2is

reference gas for determining climate changes etc.

Environmental impacts:

1. Global warming and the resulting climate changes are processes caused by

emissions called greenhouse gas emissions, which results in increased heat

absorption in the Earth’s atmosphere, also known as radiative forcing

(Leonardo energy, 2008). All greenhouse gases (such as CO2, N2O, CH4 and

VOCs) have their own characteristics and absorb radiation in varying

proportions. In order to compare emissions, the potential of each greenhouse

gas is assessed in terms of the potential of climate changes and its reference

value is the CO2 mass needed to achieve the same absorption in the

atmosphere as of another greenhouse gas. The effect of greenhouse gas is

usually assumed within a defined long or short time period. In practice, this

period is usually (20, 100 or 500) years, most frequently it is 100 years. The

indicator of the impact of global warming and climate changes is the mass of

pollutants (kg or t), which corresponds to the mass of CO2in 100 a.

2. Acidification of soil and water occurs due to the conversion of pollutants in

the air (especially SO2, NOX, HCl, NH3and HF) into acids (e.g. H2SO4, NO3,

etc.). This is followed by lowering the pH of rain (and fog as well) to 4 or

even lower. The most known consequence of acidification is dying of forests.

The indicator of the impact is given with the mass corresponding to the mass

of SO2and is described as the ability of a certain substance to generate H+

ions.

100

3. Photochemical formation of oxidants is a result of chemical reactions

NOXand volatile hydrocarbons in the presence of light. The impact indicator

of photochemical formations of oxidants is expressed using the reference

mass of ethylene (C2H4).

4. Poisoning terrestrial ecosystems relates to toxic substances emitted into the

air, water, soil or ecosystems. The potentials are calculated according to the

European model of toxicology (BRE, 2005). The reference unit for the

indicator is the mass of 1.4-dichlorobenzene.

5. The growth of biomass is enrichment with nutrients in a specific place. The

growth can be terrestrial or aquatic. It is mainly a result of pollutants in the air

and water, waste and fertilizers. This leads to an increased growth of algae in

the water, which prevent the penetration of sunlight into the depths, which

results in a reduced performance of photosynthesis and a decreased

production of oxygen, which is also needed for the decomposition of

organisms. Because of both consequences, the concentration of oxygen in the

water can be reduced in such an extent that it causes death of organisms and

the formation of methane and H2S as a result of anaerobic decomposition,

which leads to ecosystems ceasing to exist. The indicator of the growth of

biomass is equivalent to the mass of phosphate.

6. The impact on the poisoning of the people is expressed using the reference

mass corresponding to the mass of 1.4-dichlorobenzene, without taking into

account the quality of indoor air.

7. Ozone in the stratosphere (between 15–40 km above the Earth’s surface)

protects against UV radiation; in lower parts (troposphere) it is also known as

summer smog, which is toxic to living creatures if in high concentrations.

The thinning of the ozone is caused by chemicals containing chlorine. Due

to the thinning of the ozone layer, the penetration of UV rays on the Earth’s

surface increases. The model for assessing the impact was developed by the

World Meteorological Organization and is defined as a potential of various

gases in comparison to the reference substance, CFC-11. Halogenated

101

hydrocarbons are less concerning today because their use is prohibited with

the Montreal Protocol. N2O emissions are the main source of ozone thinning

on at the global level.

8. The poisoning of aquatic ecosystems is associated with surface water as a

result of emissions of toxic substances. The indicator is expressed with a

reference unit of 1.4-dichlorobenzene.

102

ANNEX 4

TEST REPORT

Contractor: ERICo

Location of sampling: Koper

Date of sampling: 11.3.2013

The date of receipt of the samples: 12.1.2015

The type of samples: sediment

Sample code: mixed marine sediment Results of the test report - mixed marine sediments

PARAMETER METHOD RESULT UNIT MU

(%)

TEST

DATES

Barium - Ba BS EN ISO 17294-2:2005 mod. #121 mg/kg s.s. / 2.2.2015

Chromium - Cr BS EN ISO 17294-2:2005 mod. #107 mg/kg s.s. / 2.2.2015

Copper - Cu BS EN ISO 17294-2:2005 mod. #28.7 mg/kg s.s. / 2.2.2015

Molybdenum -

Mo

BS EN ISO 17294-2:2005 mod. #1.80 mg/kg s.s. / 2.2.2015

Nickel - Ni BS EN ISO 17294-2:2005 mod. #80.6 mg/kg s.s. / 2.2.2015

Antimony - Sb BS EN ISO 17294-2:2005 mod. #<1.0 mg/kg s.s. / 2.2.2015

Selenium - Se BS EN ISO 17294-2:2005 mod. #0.87 mg/kg s.s. / 2.2.2015

Zinc - Zn BS EN ISO 17294-2:2005 mod. #87.7 mg/kg s.s. / 2.2.2015

Tin - Sn BS EN ISO 17294-2:2005 mod. #<5.0 mg/kg s.s. / 2.2.2015

Beryllium - Be BS EN ISO 17294-2:2005 mod. #1.11 mg/kg s.s. / 2.2.2015

Boron - B BS EN ISO 17294-2:2005 mod. #<800 mg/kg s.s. / 2.2.2015

Cobalt - Co BS EN ISO 17294-2:2005 mod. #12.7 mg/kg s.s. / 2.2.2015

Silver - Ag BS EN ISO 17294-2:2005 mod. #0.31 mg/kg s.s. / 2.2.2015

Thallium - Tl BS EN ISO 17294-2:2005 mod. #0.36 mg/kg s.s. / 2.2.2015

Vanadium - V BS EN ISO 17294-2:2005 mod. #104 mg/kg s.s. / 2.2.2015

Iron - Fe BS EN ISO 17294-2:2005 mod. #32812 mg/kg s.s. / 3.2.2015

Tellurium - Te BS EN ISO 17294-2:2005 mod. #200 mg/kg s.s. / 2.2.2015

Dry substance BS ISO 11465:1996/Cor 1:2005 98.4 mg/kg s.s. / 22.1.2015

# - results refer to a non-accredited activity

Measurement uncertainty is calculated from the contributions of uncertainty,

originating from the test methods and environmental conditions, as well as from

short-term contributions of the tested subject, in accordance with document EA-3/02.

The uncertainty is stated as the standard deviation, multiplied by a factor of two.

Measurement uncertainty is given relative to the measured quantity.

103

TEST REPORT

Contractor: ERICo

Location of sampling: Luka Koper

Date of sampling: 18.12.2014

The date of receipt of the samples: 18.12.2014

The type of samples: monolithic waste

Sample code: brick Results of the test report - brick

PARAMETER METHOD RESULT UNIT MU

(%)

TEST

DATES

leachability BS EN 12457-4: 2004 I101-1955/14 / 7.1.2015

mass of the leachate

sample

BS EN 12457-4: 2004 100 g / 6.1.2015

the volume of leachate BS EN 12457-4: 2004 1000 l / 6.1.2015

Dry substance – based

on a new sample

BS-TS CEN/TS 15414-

2:2010

99.7 % / 23.12.2014

I101-1955/14 - leachates

pH value BS 10523: 2008 8.8 / 0.14 7.1.2015

T with pH BS 10523: 2008 21.9 oC / 7.1.2015

specific electrical

conductance – SEP

(T=25,0 oC)

BS EN 27888: 1998 1240 us/cm 7 7.1.2015

T with SEP BS EN 27888: 1998 24.7 oC / 7.1.2015

Mercury – Hg BS EN ISO 12946:2012,

chapter 7

<0.20 ug/L / 9.1.2015

Antimony - Sb BS EN ISO 17294-2:2005 <0.2 ug/L 11.0 20.1.2015

Arsenic - As BS EN ISO 17294-2:2005 27.9 ug/L 8.8 19.1.2015

Copper – Cu BS EN ISO 17294-2:2005 <1.0 ug/L 13 19.1.2015

Barium – Ba BS EN ISO 17294-2:2005 <3.0 ug/L 5.3 19.1.2015

Beryllium – Be BS EN ISO 17294-2:2005 45.2 ug/L 3.4 19.1.2015

Zinc – Zn BS EN ISO 17294-2:2005 4.9 ug/L 15 19.1.2015

Cadmium - Cd BS EN ISO 17294-2:2005 <0.5 ug/L 15 19.1.2015

Cobalt – Co BS EN ISO 17294-2:2005 <0.2 ug/L 4.4 19.1.2015

Tin - Sn BS EN ISO 17294-2:2005 <1.0 ug/L 6.1 20.1.2015

Chromium – Cr BS EN ISO 17294-2:2005 191 ug/L 12 19.1.2015

Nickel – Ni BS EN ISO 17294-2:2005 3.9 ug/L 12 19.1.2015

Selenium – Se BS EN ISO 17294-2:2005 <10.0 ug/L 18.0 19.1.2015

Silver - Ag BS EN ISO 17294-2:2005 <1.0 ug/L 14.2 19.1.2015

Lead – Pb BS EN ISO 17294-2:2005 <0.5 ug/L 16 19.1.2015

Vanadium – V BS EN ISO 17294-2:2005 <200(1113) ug/L 6.8 22.1.2015

Boron - B BS EN ISO 17294-2:2005

modified

#681 ug/L 20 10.2.2015

Thallium – Tl BS EN ISO 17294-2:2005

modified

#<1.0 ug/L 20 19.1.2015

Tellurium – Te BS EN ISO 17294-2:2005

modified

#<10.0 ug/L 20 19.1.2015

Chromium – Cr (VI) BS ISO 11083:1996 0.17 mg/L / 16.1.2015

Iron – Fe BS EN ISO 17294-2:2005

modified

#<10.0 ug/L 20 19.1.2015

Chloride ISO 10304-1:2007 >50(79.6) mg/L 12 28.1.2015

Sulfate ISO 10304-1:2007 670 mg/L 10 28.1.2015

# - results refer to a non-accredited activity

104

Waste leachate is analyzed in accordance with BS EN 16192:2012. Sample

preparation was carried out according to standard BS EN 15002: 2006.

Measurement uncertainty is calculated from the contributions of uncertainty,

originating from the test methods and environmental conditions, as well as from

short-term contributions of the tested subject, in accordance with document EA-3/02.

The uncertainty is stated as the standard deviation, multiplied by a factor of two.

Measurement uncertainty is given relative to the measured quantity.

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