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Investigation of (BOF) converter slag use for agriculture in Europe

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Metall. Res. Technol. 111, 155–167 (2014)

c EDP Sciences, 2014 Metallurgical Research
DOI: 10.1051/metal/2014022
&Technology
www.metallurgical-research.org

Investigation of (BOF) Converter slag

use for agriculture in europe
T. Annunziata Branca1, C. Pistocchi1,2, V. Colla1 , G. Ragaglini1,
A. Amato1 , C. Tozzini1, D. Mudersbach3, A. Morillon3, M. Rex4
and L. Romaniello5
1
Scuola Superiore di Studi Universitari & di Perfezionamento Sant’Anna, Pisa, Italy
e-mail: t.branca@sssup.it
2
Group of Plant Nutrition, ETH Zurich
3
FEhS-Institut für Baustoff-Forschung e.V., Bliersheimer StraBe 62, 47229 Duisburg, Germany
4
Arbeitsgemeinschaft Hüttenkalk e.V.,
5
ILVA S.p.A, ILVA Steelworks, Taranto, Italy

Key words:
Slag; fertiliser; soil; crops;
lysimeter; liming material;
thomasphosphate; metals
Received 28 January 2014
Accepted 18 April 2014
Abstract – The goal of zero-waste is one of the main challenges of modern steel industry,
which over the past 20 years has been committed to increase the recovery and the use of
by-products generated during the ironmaking and steelmaking processes. Among the main
by-products generated during iron and steel production, such as slags, dusts and sludges,
slags constitute about 90% of the total. Slags are currently used in various fields (such as ce-
ment production, road construction, environmental recovery in landfill covers, as fertilizer
and soil conditioner, etc.) according to their chemical features, which depend on production
process origin. In Italy, in particular for example, BF (Blast Furnace) slag is used for cement
production while BOF (Basic Oxygen Furnace) slag without iron (inert slag) is used as landfill
cover, in compliance with Italian legislation. In Germany, BF and BOF slag use as fertlisers
and liming materials has a long tradition. Although in recent years slag use has increased,
the application for agriculture purposes needs to be further investigated. Slag can be used
as a soil conditioner (high content of Ca and Mg), Si supply (improves the crops resistance to
pests and diseases), P fertilizer production and micro-nutrients supply. Use of slags can af-
fect human health and environment, because of heavy metal content, which can leache to
groundwater or be transferred to surface water. The assessment of risk to the environment
based on slag application requires further investigation. This represents an opportunity for
both the steel and fertilizer industries to promote natural resources savings, CO2 emission
reductions, landfill waste prevention as well as social awareness of sustainability of some in-
dustrial activities. The BOF slag has been shown to be useful as liming material for acidic soil
amendment and it can replace commercial fertilizers. Different effects on crop yields and
on soil parameters can be found, depending on soil characteristics and climate conditions.
In Middle Europe, with humid climate, lime losses through leaching of up to 0.5 t CaO/ha
have to be replaced with liming material to prevent acidification. Evaluation of long-term
field trials with slag liming materials can give information about the impact of slag applica-
tions on crop management and the environment. In Mediterranean regions, such as in Italy,
arable soils rarely show acidic characteristics. Alkaline soils from coastal areas are often rich
in sodium content, due to seawater intrusion and irrigation with saline water. The aim of
this research is also to investigate the application of BOF slag to these soils, in order to as-
sess the effect of Ca contained in slag in balancing negative Na effects. This paper is based
on the preliminary study and experiments carried out within an ongoing RFCS (Research
Fund for Coal and Steel) project.

n recent decades waste management has increasing costs. On the other hand, the goal

I become an important environmental is-

sue, due to the increase of industrial by-
products and wastes as well as municipal
waste generation. This has led to the growth
of their use as an alternative to disposal, in
order to avoid landfill areas exploitation and
to decease consumption of natural raw re-
sources results in a more sustainable use of
industrial by-products and wastes.
During the iron and steelmaking pro-
cesses significant quantities of by-products
are produced, such as slags, dusts and

Article published by EDP Sciences

 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)
sludges. Large amounts of them have been
recovered or recycled over the years. By-
products can be internally recycled, but
some by-products can also be converted into
forms to be used in other industries [1].
Nevertheless, some fractions continue to be
disposed in landfills. Due to technology
changes, new material specifications and
more restrictive legislation, it has become ur-
gent to address the new issues arisen. The
steel industry commitment is focused on
achieving the principle of resources conser-
vation and on enhancing the sustainability
of ironmaking and steelmaking processes.
The challenge is to make by-products suit-
able for internal reprocessing or use in other
industries, in order to minimise their dis-
posal in landfills. This can be carried out by
promoting effective research programmes
and through a positive approach coming
from environmental regulators [2].
From the chemical point of view steel
slags are complex matrices consisting of
compounds usually similar to those present
in the environment, such as oxides of Si, Ca,
Mg, Fe and Mn in complexes of calcium sil-
icates, aluminosilicates and aluminoferite.
According to Worldsteel Association [3]
the BOF slag destinations are globally as fol-
lows: external recovery (58%), internal re-
covery (23%), internal landfill (11.5%), inter-
nal stockpile (7%).
BOF slag can be recycled and, in many
plants all over the world, it is currently
100% recycled. It can be used in many ap-
plications, such as cement industry, as acidic
soil conditioner, as marine environment-
improving material, as railroad ballast and
as concrete aggregate. Some chemical com-
ponents, such as S, P and Cr total can rep-
resent problems for e internal BOF slag re-
cycling. Other components, such as F and
Cr(VI) can limit its external recycling, due to
the limitations imposed by the environmen-
tal legislation. This leads to increase in land-
fill and consequently to increase in costs.
Both external and internal recovery issues
of BOF slag require not only industrial and
market competences, but also research and
technical solutions.
By considering the possible uses of met-
allurgical slags, because of their chemical
and physical properties, this paper pays
156
special attention to BOF slag use for agri-
culture purposes [4] and is based on the pre-
liminary study and experiments carried out
within an ongoing RFCS (Research Fund for
Coal and Steel) project.
1 Legislation outline
Slags are definitely not a waste, for both their
chemical and physical properties and their
possible applications as valuable materials
in different fields.
Over the past 25 years, although the use
of slags has been a consolidated practice,
particularly in construction, the discussion
has been focused on the slag classification
as a waste or as a by-product. After the
revision of the Waste Framework Directive
2008/98/CE-WFD in 2008 [5], better defini-
tions of waste and by-product have been in-
troduced in Article 5 (which defines the con-
ditions of criteria to classify a material as a
by-product) and Article 6 (which defines the
conditions that allow a material to cease to
be a waste). In light of these new clear defini-
tions, ferrous slags can be considered, as fol-
lows: as a by-product in its liquid state, with
or without further processing; as a waste, but
it ceases to be waste after recovery measures.
The classification of ferrous slags is
not uniform in European countries, as in
some Member States are considered as by-
products, in others as wastes. For this rea-
son there is the need to harmonize the Eu-
ropean standards. On this subject Euroslag
developed in 2006 a position paper, aiming
to show how slag is a product and not a
waste [6]. In 2011 it developed a position pa-
per concerning the classification of ferrous
slag based on prerequisites provided by the
Waste Framework Directive [7].
Concerning the use of slag, the other
most representative European directives
and regulations are, as follows: EU-Waste
catalogue (2000), EU-Council Decision on
the Landfill of Waste (2002), EU-Waste
Shipment Regulation (2006), EU-REACH
Regulation (2006), EU-Construction Prod-
uct Regulation (2011). In particular, the EC
Regulation No 1907/2006, concerning Reg-
istration, Evaluation, Authorisation and Re-
striction of Chemicals (REACH) [8], has im-
posed to European producers and importers
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)
the study of physical and chemical, toxico-
logical and eco-toxicological properties of
the substances produced or imported, in or-
der to have a special registration dossier to
ECHA, the European Chemicals Agency. In
order to address the REACH registration of
slag, the European steel industry, in agree-
ment with Eurofer, has formed the Consor-
tium RFSC (REACH Ferrous Slag Consor-
tium), which is scientifically driven by the
German Institute FEhS (Research Institute
for Iron and steel slags). It aims at preparing
a single registration dossier and at investi-
gating the behaviour of iron and steel slags
on the human health and on the environ-
ment, starting from the assumption that in
general slags are not waste.
According to the REACH Regulation,
it has been agreed to classify the slag as
UVCB substance, namely as a substance of
variable composition, produced by a com-
plex reaction, in order to maintain a uni-
formity of classification and to expand the
field of investigation on toxicological and
eco-toxicological effects. Based on the data
already available, in order to achieve the
REACH registration, the RFSC Consortium
has subdivided the steel slags, depending
on their origin, into four families. Each fam-
ily is identified with its own CAS- and/or
EINECS-numbers, as follows: the blast fur-
nace (BF) slag, including ABS (Air-cooled BF
Slag) and GBS (Granulated BF Slag), steel
slags, including BOS (Basic Oxygen furnace
Slag), EAF C (Electric Arc Furnace slag, from
Carbon steel production), and EAF S (Elec-
tric Arc Furnace slag, from Stainless/high al-
loy steel production), and finally SMS (Steel-
making Slag). The families SMS and EAF S
include secondary metallurgical slag.
2 Overview of the project
The results presented in this paper have been
derived from RFSR-CT-2011-00037 project
“Impact of long-term application of BF and
steel slags as liming materials on soil fer-
tility, crop yields and plant health”. Aim-
ing at increasing the use of iron and steel
slags for agriculture purposes, it is focused
on the improvement of the environmental
and economic aspects. This will contribute
to make the European steel industry more
sustainable, through conservation of natural
resources and reduction of spaces needed
for landfilling the slag fractions that are not
reused. Iron and steel slags have been al-
ready used for a long time as fertilisers and
liming agents in Northern Europe, such as
Germany and Scandinavia. Previous stud-
ies [9] have shown how BF and steel slags
positively affect plant and crop yields; how-
ever the concentration of Cr and V increases
in the soil, but they are bound in the top soil
without affecting the groundwater. This was
the starting point for further investigation
on the long term effect. Along with long-
term field trials using Thomas slag, BF and
converter slag, new field experiments with
converter and ladle slag applications have
been designed in Germany, in order to as-
sess the liming effect of slags on soils and
plants.
In Italy acidic conditions rarely occur on
agricultural soil, while many agricultural ar-
eas in the coastal plains are characterized by
sodicity of soil and irrigation water, due to
the intrusion of marine water. BOF slag (rich
in CaO and MgO) was used to reduce the
ESP (Exchangeable Sodium Percentage) lev-
els in saline-sodic soils. The aim is to lower
the Na sorption of soil exchangeable com-
plex by addition of Ca and Mg. The experi-
ment is carried out in lysimeters in order to
evaluate also the risk of heavy metals leach-
ing in groundwater when BOF slag is ap-
plied to the soil. This kind of experiment has
not been carried out so far. Only laboratory
leaching tests on slags have been made in
order to study the slag behaviours [10, 11].
The achieved results will be useful not
only to improve the knowledge of slag use
in agriculture, but also to better understand
what the critical issues from the environ-
mental perspective are, in order to allow fur-
ther uses of iron and steel slags in other fields
of application, such as building industry and
road construction.
The added value of this research con-
cerns several research activities that have
been carried out in different European coun-
tries, through the implementation of dif-
ferent tests, depending on local conditions.
They are connected not only to the different
climate and soil conditions, but also to the
local economic, environmental and legisla-
tive background of each involved country.
157
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)
3 German experimental
field trials
In Germany Thomasphosphate had been
used successfully as a fertiliser for more
than 100 years. It is no longer produced
and other currently produced slag fertilis-
ers/liming materials have to be investigated
for their long term-effects on the environ-
ment and plants. Three long-term field tri-
als are restarted or continued as part of
SLAGFERTILISER project which are located
in west (Rösrath), middle (Essershausen)
and south (St. Peter) of Germany. The
test fields have been running since 1954
in St. Peter, 1990 in Rösrath and 1993 in
Essershausen.
The grassland P fertilisation experiment
was installed in 1954 in St. Peter (Black
Forest) 744 m above sea level on a Dystric
Cambisol of Gneiss geological origin. Two
different P fertilizers, Thomasphosphate and
soft rock phosphate, should be introduced to
agricultural practise in this mountain region.
Although Thomasphosphate is no longer
produced the continuation of this trial is
valuable to investigate the impact of long-
term annual slag application on soil fertility
and plant quality under field conditions. Es-
pecially the influence of Cr and V accumu-
lation in the soil shall be analysed.
The field trial was started with 3 treat-
ments with 4 replicates each: a control with-
out phosphate, Thomasphosphate and soft
rock phosphate all without additional lim-
ing. The over time decreased pH values led
in 1985 to the decision to add an additional
liming with carbonate limestone on two of
the replicates of each treatment to equal-
ize the different pH values. From 2001 un-
til 2009 Thomasphosphate was replaced by
Dicalcium phosphate or Triple superphos-
phate combined with converter lime in a
P/CaO relation similar to Thomasphosphate.
Since 2010 we had again access to a reserve
of Thomasphosphate.
Another field trial on grassland with a
more intense use (4−5 cuts annually) than in
St. Peter was established in 1990 in Rösrath
nearby Cologne. In this trial the effects of
liming on plants and soil of two liming ma-
terials on two levels each are compared.
Besides a control without liming two dif-
ferent liming materials are applied on two
158
lime levels: a carbonate magnesium lime-
stone and converter lime from disintegrated
BOF slag. In this trial the impact of long-term
application of converter lime in comparison
to carbonate limestone is investigated un-
der intense grassland use. Each treatment
is replicated four-fold. The trial was started
first with high annual lime amounts to reach
an optimum pH level. Afterwards the lime
application was reduced to an amount of
preservation liming on the higher lime level.
On the lower liming level half of this amount
was applied. There will be also investiga-
tions of heavy metal accumulation and up-
take by grassland vegetation.
The third long-term field trial has been
installed 20 years ago on arable land in
Essershausen in northern Taunus region
about 50 km north of Frankfurt. It is an-
other liming trial. Five different liming mate-
rials are compared in this trial on one liming
level: carbonate limestone, burnt lime, blast
furnace lime and two converter limes, one
of disintegrated LD slag and one of milled
LD slag. As in Rösrath the trial started with
high annual amounts of lime of 1 to 2 tons
CaO ha−1 to reach the optimum pH level. Af-
ter that the lime application was reduced to
500 kg CaO ha−1 year−1 as preservation lim-
ing. Since 1993 when the trail was started
up to now 14.8 tons CaO ha−1 were applied.
This had not only influence on the soil reac-
tion but also on the input of calcium, mag-
nesium, silicates and other nutrients. This
supply with elements being involved in the
condition of soil structure has influence on
the physical properties of the soil which
will be investigated. With the liming of con-
verter lime within the last 20 years about
45 kg Cr ha−1 and about 50 kg V ha−1 were
applied. The impact of this continuous sup-
ply on soils shall be investigated, especially
the bindings of Cr and V and the changes
of chemical and mineral bonding of these
elements.
4 Italian trial
Although the use of steel slags on arable
soil, due to their liming potential in acidic
soil, has a long tradition in Europe, only
few studies have been carried out on their
use in neutral or alkaline soils [12] present
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)
Table 1. Soil exchangeable cations, cation ex-
change capability (CEC) and exchangeable
sodium percentage (ESP) after salt addiction.
Parameter Mean st. dev. n with respect to the stoichiometric Ca amount
Cae mg/kg 718.0 100.8 10
Mge mg/kg <20 <20 10
Nae mg/kg 450.5 91.1 10
Ke mg/kg 216.6 8.4 10
CEC meq/kg 99.5 21.3 10
ESP % 39.4 11.1 10
in Mediterranean regions. Alkaline soils in
some coastal areas are affected by sodicity,
due to sea water infiltration and irrigation
with saline water. ESP has been used as in-
dicator of soil sodicity. Sodicity can directly
affect crop growth, because of Na toxicity for
plants, and indirectly, acting as deflocculant
on soil colloids (e.g. clays). The trial carried
out in Italy aimed at assessing the potential
in reducing the sodicity through the use of
BOF slag, coming from the ILVA steelworks,
the largest integrated steelworks in Europe.
A lysimeter trial has been set up, using differ-
ent levels of BOF slag application on saline-
sodic soils cultivated with tomato (Lycop-
ersicon esculentum L.) and potato (Solanum
tuberosum L.) crop and irrigated with saline
water.
Each lysimeter is a polyethylene box of
1.00 m depth and 1.00 × 1.00 m surface,
equipped with an automatic drip irrigation
system and a plastic tank to collect drainage
water. The soil texture is loamy sand, accord-
ing to the USDA classification, and pH is
slightly alkaline (around 7.5).
Before planting, the soil was treated
with salt, in order to mimic saline-sodic
conditions. According to a completely ran-
domised experimental design with three
replicates (for a total of 24 lysimeters), the
upper 25 cm of soil were mixed with solid
NaCl in a proportion of 1.5 g NaCl per kg of
soil. This proportion was calculated in order
to achieve an ESP of almost 35% (sodic con-
ditions). After the treatment, 10 soils sam-
ples were randomly chosen and analysed for
exchangeable cations from which ESP was
calculated. The results are shown in Table 1.
Subsequently, three slag doses, D0, D1
and D2 (0, 3.5 and 7 mg/kg, respectively)
were manually supplied and mixed in the
upper 10 cm of soil. In addition, a blank
treatment (tap water irrigation without slag)
with three replicates was set up. The D1
and D2 doses were calculated in excess
needed to reduce the ESP to a value be-
low 5%. Calcium can precipitate in the soil
(e.g. as calcium carbonate or silicates) and
be less available to exchange with Na on the
sorption sites.
At the end of May, tomato (var.
Riogrande) and potato (var. Almera)
seedlings were planted with a density of 6
and 8 plants/m2 , respectively. Nitrogen and
K fertilisers were supplied at transplanting,
according to recommended doses for the re-
gion and equivalent to 0.35 tons/ha of urea
and 0.86 tons/ha of potassium sulphate.
During the growing season the volume
of irrigation water was equal to 0.52 m3
per lysimeter, corresponding to 520 mm
and the total rainfall was 100 mm. NaCl,
MgCl2 and MgSO4 were added to irriga-
tion water in order to attain the salinity
of 5 mS/cm. Drainage was sampled when
2 L were reached, corresponding to 5% of
field capacity. For each sampling, after the
drainage volume measurement, two sub-
samples were collected in acid-washed PTE
bottles in order to analyse major cations (Ca,
Mg, Na, K), nitrates (NO3 ), chlorides (Cl)
and trace metals (Cr, CrVI and V). Electric
Conductivity (EC) and pH were measured at
the sampling time with portable devices. A
field blank was also prepared for each sam-
pling. Samples were stored at 4 ◦ C before
analyses. In this paper the results concerning
the drainage produced during the summer
season (only one significant rain event) are
presented.
During the harvest (on 4 September and
10 October for tomato and potato, respec-
tively) 5 replicates of the aboveground, roots
and edible part -biomass, were collected
for each lysimeter. After collection the sam-
ples were oven-dried at 60 ◦ C until constant
weight. Weeds also were sampled and the
dry biomass determined. The analyses of
metal content in the plant tissues are ongo-
ing, for this reason here we present only the
production results.
In the early autumn, after the harvest
of the two crops, soils sampling was car-
ried out. For each lysimeter 3 samples were
159
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)
Table 2. Yields in a long-term grassland trial in St. Peter, Black Forest, Germany.
without Thomas-
phosphate phosphate phosphate phosphate phosphate phosphate
without additional lime
Yields
mean yields 1954-2012 38.8 70.3
mean yields 1985-2012 52.3 93.2
mean yields 2011-2012 52.2 75.8
yields 2012 56.1 79.7
Results of soil investigations after last harvest 2011
ph values 2012 4.2 4.6
CAL-P2 O5 (mg 100 g−1 ) 8.0 14.0
collected at two different depths (0−10 and
10−30 cm). A composite sample for each
layer was air-dried and analysed for ex-
changeable cations, trace metals, anions and
available P.
A two-way ANOVA has been performed
on the drainage concentrations, using crop
(2 levels) and dose (4 levels) as orthogo-
nal factors. A three-way ANOVA has been
performed on soil data, using crop (2 lev-
els), soil layer (two levels) and dose (4 lev-
els) as orthogonal factors. Tuckey HSD
test has been used for the post-hoc means
comparisons. Data analyses of tubers and
barriers production per plant, as well as
above ground-biomass (AGB), roots weight
and weeds biomass were carried out by one
way ANOVA and orthogonal contrasts con-
sidering slag treatments as factor.
All tests were performed with R sta-
tistical software (version 2.12.0, R Founda-
tion for Statistical Computing, http://www.
r-project.org).
5 Discussion
5.1 German field trials
The long-term P fertilisation and liming in
the German long-term field trials had a
strong effect on the yields of grassland and
arable crops. This was particularly clear in
the 60 years old field trial with Thomaspho-
sphate in St. Peter (Tab. 2). The phosphate
fertilisation had a positive influence on the
dry matter yields of the grassland. The per-
manent annual Thomasphosphate applica-
tion led to an increment of 30 dt grassland
dry matter/ha in comparison to the yield on
160
Rock- without Thomas- Rock-
Isd5%
with additional liming
Yields in dt D.M./ha
61.5 46.8 72.3 64.8 0.3
80.3 68.6 96.1 86.5 0.5
69.5 66.3 90.2 80.5 10.3
78.8 77.6 104.8 93.3 12.5
4.4 5.8 5.6 5.8 0.2
18.5 2.5 10.0 4.0 4.4
the control treatment and a surplus of about
10 dt D.M./ha compared to the Rockphos-
phate fertilisation. As in the course of this
trial [13] the highest yields on the Thomas-
phosphate treatments remained until now.
Table 2 shows the nearly equal pH values
in the soil of the treatments with additional
liming, which are on a significant higher
level than soil pH without additional lim-
ing. Liming induced a significant yield in-
crease particularly with the treatments with
Rockphosphate and the one without P fertil-
isation while there was no real difference in
yields of the Thomasphosphate treatments
with and without additional liming except in
2012. P fertilisation with Thomasphosphate
means also liming because of a neutralis-
ing value of this fertiliser of 45% CaO. The
higher yields in the treatments with addi-
tional liming and the higher nutrient uptake
compared to the part without additional lim-
ing caused a depletion of nutrients in the soil
especially in phosphate.
The different yields resulted not only
from the better growth of plants, but also
from different phytosociological composi-
tions of the grassland which influenced also
the quality of the fodder (Tab. 3). The phos-
phate fertilisation particularly with Thomas-
phosphate had a positive effect on the ap-
pearance of legumes, herbs and grasses of
high fodder quality. The additional liming
also stimulated the appearance of herbs
and legumes already shortly after start-
ing the additional liming [14]. Based on
the phytosociological composition of the
sward and the yields a value numeral was
calculated. The highest number and the
highest fodder quality is still determined
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)

Table 3. Composition of grassland and yield fodder value numeral according to MOTT [15].

without Thomas- Rock- without Thomas- Rock-

phosphate phosphate phosphate phosphate phosphate phosphate
2011 without additional lime with additional liming
Proportion (%)
Herbs 15.1 26.1 21.1 23.1 18.6 15.1
Legumes 0.0 8.5 4.0 1.5 5.5 0.0
Grasses 85.0 65.5 75.0 65.5 76.0 85.0
Foddes value numeral
Herbs 51 95 77 102 68 63
Legumes 0 60 27 11 38 0
Grasses 315 349 364 389 479 475
Yields (dt/ha) 48.2 71.9 60.1 54.9 75.5 67.7
Yield fodder
value numeral1) 207 426 331 324 519 428

Table 4. Chromium contents in the soil profile of the long-term field experiment St. Peter (Black
Forest) 60 years after beginning of the trial.

Soil without phosphate Thomasphosphate Soft rock phosphate

depth unlimed limed unlimed limed unlimed limed lsd5%
Chromium content in the soil (mg Cr/kg)
0−5 cm 43.6 31.6 84.2 70.9 44.5 31.7 23.1
5−10 cm 43.7 29.8 72.6 58.5 42.6 29.2 11.7
10−15 cm 42.3 27.2 62.4 56.5 38.9 30.1 7.6
15−20 cm 41.3 26.4 56.2 50.7 39.4 27.3 12.0
20−25 cm 42.7 26.6 45.2 42.3 38.4 26.2 13.0
25−30 cm 44.1 24.9 43.3 36.3 40.6 23.3 19.6
30−35 cm 40.0 23.9 49.1 27.0 42.6 22.2 26.8
35−40 cm 38.1 22.4 44.0 30.3 36.3 24.2 24.2
40−45 cm 41.6 21.9 40.0 25.9 35.2 22.7 24.9
45−50 cm 40.8 20.1 33.6 21.4 33.8 23.0 23.3

on the Thomasphosphate treatment. Addi-
tional liming improved the yield fodder
value numeral on all treatments.
The continuous annual application of
Thomasphosphate involved an increase of
Cr in the soil. This field trial on permanent
pasture without soil cultivation opens the
possibility of further investigations of the
mobility of Cr in the soil profile. 60 years
after the initialising of the trial Cr was signif-
icantly enriched in the top soil (Tab. 4). This
enrichment was detectable until a soil depth
of 25 cm on both liming treatments. The two
replicates of all three treatments with addi-
tional liming are located on one side of the
experiment. Obviously the geological origin
of the soil is somewhat different and its Cr
content is lower than in the soil of the trial
on the unlimed side. The displacement of the
enriched Cr was probably caused by biotur-
bation and less by leaching as this was ob-
served in the soils of trials on arable land [9].
In the field trial on the other grassland
site in Rösrath liming with both liming ma-
terials increased the dry matter yields of the
grown grassland (Tab. 5). From the unlimed
control to the highest lime application level
there is a clear slope of the growth curve as
well in the last years yields as in the mean
yields of the total duration of 23 years. The
mean yields are significantly higher on the
treatment with disintegrated converter lime.
The liming effect on soil pH of both products
was similar. There are significant increases
of pH from the control to the first and to the
second liming level but no significant differ-
ences between the pH values of both liming
materials on the same liming level.
The analyses of soil samples from the
field trial Rösrath (depth of 0 to 10 cm)
showed a clear increase of Cr in the plots
with converter lime application (Fig. 1). The
total Cr determined by means of alkaline
melt was about 90 mg/kg Cr and it was
161
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)

Table 5. Yields and soil pH values in a long-term grassland trial in Rösrath near Cologne, Germany.

Unlimed Carbonate Mg-Limestone Converter lime (disint.)

kg CaO ha−1 0 Ø 289 Ø 578 Ø 289 Ø 578
Yields (dt D.M./ha∗y ) lsd5%
2012 (4 cuts) 137.6 140.5 148.1 144.2 146.5 11.6
Ø 1990–2012 107.7 112.5 114.3 115.9 117.8 1.7
soil pH (CaCl2 )
2011 5.40 5.78 6.18 5.88 6.28 0.3
Ø 1990−2011 5.34 5.98 6.34 5.96 6.32 0.2

120 120

mobile NH4NO3-extractable Cr (µg/kg Cr)

Alkaline melt
100 100
Chromium in the soil (mg/kg Cr)

80 80

60 Aqua regia 60

40 40
without lime
CaO 1 (Carbonate limestone)
20 CaO 1 (Converter lime disintegrated) 20
NH4NO3-extractable

0 0
0 2 4 6 8 10 12 14
Experimental year

Fig. 1. Total, aqua regia and NH4 NO3 extractable chromium in the soil of the liming trial on
grassland in Rösrath.

increased to about 10 mg/kg Cr by converter liming materials were furthermore higher

lime application. Aqua regia extractable Cr than yields on the treatments with carbon-
constituted about 50% of the total Cr. Its in- ate limestone and burnt lime. In the last year
crease by converter lime seems to be higher oats were harvested with problems, because
than of the total Cr. A great variability exists of heavy lodged grain. This led to a high
due to the part of not yet transformed con- variability of yields and a high least signif-
verter slag taken with the soil samples. Up icant difference. However the oats yields of
to now there are no indications of a negative 2012 show similar relations with the grada-
influence of the Cr accumulation on soil fer- tion of the long-term yields except for the
tility. The solubility of Cr in converter slag is treatment with disintegrated converter slag.
very low as it is minerally bonded in poorly
Application of the two converter limes
soluble compounds as spinels. That is the
from disintegrated and milled BOF slag in-
reason that mobile Cr in the soil is very low
creased V content in the soil (Fig. 2). Due
even after its accumulation. The NH4 NO3 -
to the soil cultivation on this arable land
extractable Cr in the field trial was on a level
the applied V was incorporated into the top
of about 10 µg/kg Cr with no significant dif-
soil through ploughing, to a depth of about
ferences between the unlimed control and
30 cm. The resulting in lower V content than
the two liming treatments.
on the grassland soils. The variability of the
The mean yields of crops in the 20 years total alkaline melt digested V was similar
old liming trial on arable land in Esser- to that of Cr variability on grassland. With
shausen were significantly increased by aqua regia only 50% of the total V was ex-
liming with all different liming materials tracted. The soil samples of the converter
(Tab. 6). Yields on the treatments with silicate lime treatment showed a clear increase of
162
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)

Table 6. Mean yields of total experimental time, yields 2012 and soil pH values in the long-term
field trial Essershausen on arable land.
blast disintegrated milled
without burnt carbonate furnace converter converter
Liming material
lime lime limestone lime lime lime
Ø kg CaO ha−1 a−1 0 740 740 740 740 740
Year Crop Yields (dt GE ha−1 a−1 ) Isd5%
2012 oats 67.8 71.3 79.5 77.4 70.1 78.5 9.9
Ø 1993–2012 71.7 76.4 77.0 78.7 78.6 79.0 1.8
Soil pH (CaCl2 )
2012 5.30 6.65 6.65 6.50 6.48 6.53 0.24
Ø 1993–2012 5.09 6.17 6.25 6.07 6.09 6.07 0.11

80
75
Vanadium Content (mg V/kg Soil)

70 Alkaline Melt

65
60
Without Lime Burnt Lime
55
Blast Furnace Lime Converter Lime disintegrated
50 Converter Lime milled
45
Aqua Regia Extraction
40
35
30
0 2 4 6 8 10 12
Experimental year
Fig. 2. Total and aqua regia extractable vanadium in the soil of the liming trial on arable land in
Essershausen.

the V content within the first 4 years with the right calculation: the bulk density, the
higher amounts of lime application. In the homogenous distribution of the applied lim-
following years with preservation liming of ing material in the plough layer or the vari-
about 500 kg CaO/ha* y, there was nearly no ability of the V in the reference soil. There
change of the V contents. is also the supposition that V and Cr in the
soil changes into bonding which are no more
With the amounts of applied liming ma-
extractable by aqua regia. This presumption
terials and fertilisers with their known con-
was expressed at the evaluation of analytical
tents of heavy metals the input of elements
data from other long-term field trials [9]. In
into the soil can be calculated. Figure 3
further analytical investigations of soil sam-
shows the calculated and measured V accu-
ples from the running long-term field tri-
mulation in the soil in relation to the V con-
als the answers to these questions will be
tents of the soils of the unlimed reference
evaluated.
treatment. As already seen in Figure 2 the
aqua regia extractable V showed an increase
in the first year which was nearly on the level 5.2 Italian trial
of the calculated increase. The calculated in-
crease of V was higher than the measured The results of the drainage analyses are
content. There are several uncertainties for listed in Table 7. The concentrations of
163
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)

10
Aqua Regia Extraction
Change of Vanadium Contents (mg V/kg )
Burnt Lime
BF Lime measured
8 BF Lime calculated
BOF Lime D measured
6 BOF Lime D calculated
BOF Lime M measured
BOF Lime M calculated
4

-2
0 2 4 6 8 10 12
Experimental year

Fig. 3. Calculated and measured changes of the aqua regia extractable vanadium contents in the
soil of the field trial in Essershausen.

Table 7. Mean values of the parameters measured in the drainage waters and relatives P value
from the ANOVA. C = control, D0 = saline irrigation water and slag dose = 0 mg kg−1 , D1 = saline
irrigation water and slag dose = 3.5 mg kg−1 , D1 = saline irrigation water and slag dose = 7 mg kg−1 .
0 = ***, 0.001 = **, 0.01 = *, 0.05 = .

crop dose pH EC Ca Mg K Na Cr V Cl NO3

µS/cm mg/l mg/l mg/l mg/l µg/l µg/l mg/l mgl
TOM C 9.37 1318 161 15.5 6.2 64.0 1.1 16.0 104.00 1.10
D0 8.58 4540 464 62.3 23.7 485.0 1.2 23.3 1220.00 0.70
D1 8.61 5523 551 94.0 42.0 517.0 1.2 29.3 1544.00 <0.1
D2 9.28 5485 606 92.0 32.0 491.0 1.2 29.5 1553.00 0.30
POT C 9.06 1488 163 35.0 13.8 63.0 0.8 21.0 104.00 6.70
D0 8.72 3590 366 54.0 16.3 328.0 0.5 23.0 858.00 11.70
D1 8.67 2933 304 49.0 26.0 218.0 0.5 20.0 534.00 59.40
D2 7.19 2930 346 49.0 35.0 208.0 0.5 27.0 574.00 112.00
crop ns ** * * ns *** *** ns ** *
dose ns ** ** ** ** *** ns * ** ns
P value Interac. ns ns ns ns ns ns * ns ns

Cr(VI) were always below the detection lim- the drainage of D0, D1 and D2 treatments
its (0.5 µg/l) and are not shown. with respect to the control (C). This is due
The pH was not affected by the treat- to the salts addition in the irrigation wa-
ments, while EC was affected by the crop and ter. Slag application did not produce any ef-
by the BOF slag levels. The controls (C) dif- fect on drainage waters (i.e no significant
fered significantly with the treatments (D0, differences among D0, D1 and D2), except
D1 and D2). This is due to the irrigation wa- for K and V. Particularly K concentration was
ter treated with salts. higher in D2 and D1 treatments compared to
The major exchangeable cations (except D0 and C; on the other hand, Cr and V con-
for K), Cr and Cl significantly differed be- centrations were higher in D2 compared to
tween the two crops, with lower concentra- the other treatments. Potassium was added
tions in the leachate of potato lysimeters. only as a fertiliser, not added with the slag
Major cations (Ca, Na, K, Mg) and Cl or irrigation water, at the same quantity for
concentrations were significantly higher in all treatments. An indirect effect was seen
164
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)

Table 8. Mean values of the parameters measured in the soils and relatives P value from the ANOVA. C = control, D0 =
saline irrigation water and slag dose = 0 mg kg−1 , D1 = saline irrigation water and slag dose = 3.5 mg kg−1 , D1 = saline
irrigation water and slag dose = 7 mg kg−1 ; U = upper soil profile, L = lower soil profile; 0 = ***, 0.001 = **, 0.01 = *, 0.05
= . levels of probability.

profile crop dose EC Polsen Cae Mge Ke Nae Cr V Cl NO3 ESP

µS/cm mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg
L TOM C 133.9 43.7 918.0 52.0 166.0 26.0 50.0 16.7 11.6 19.7 2.0
D0 155.6 42.7 828.0 46.0 182.7 184.7 54.0 19.0 13.1 29.5 13.4
D1 158.0 42.0 954.3 42.3 149.7 258.0 48.0 18.0 10.1 23.0 17.0
D2 169.5 42.0 1020.0 55.0 151.0 225.0 65.0 20.0 10.2 27.3 14.6
POT C 100.6 44.7 929.5 56.0 180.7 23.0 47.0 15.7 5.1 23.3 1.6
D0 136.7 42.0 816.0 45.3 145.0 193.3 50.3 17.0 6.5 34.7 14.5
D1 116.5 43.3 987.7 45.7 181.7 140.3 51.0 18.3 10.1 18.7 9.4
D2 119.8 43.7 1211.0 39.0 118.0 173.7 48.0 17.7 5.2 26.7 16.6
U TOM C 114.0 42.3 899.0 56.3 326.3 19.7 51.0 17.0 3.7 31.3 1.3
D0 112.1 46.0 876.3 54.3 292.3 48.7 54.0 16.5 4.8 36.3 3.0
D1 111.4 41.3 1046.7 48.0 280.3 59.7 60.7 18.3 2.7 23.3 3.0
D2 124.2 42.0 1051.0 48.7 280.0 60.0 67.7 21.0 8.9 33.3 3.6
POT C 86.1 43.7 965.7 56.3 293.3 19.7 56.7 16.7 3.7 29.3 1.3
D0 117.1 43.0 796.0 54.3 339.3 44.0 54.7 18.7 2.7 43.7 3.2
D1 119.7 45.7 1037.7 48.0 288.3 49.0 54.7 18.7 7.4 18.7 3.7
D2 114.7 40.0 1071.3 48.7 243.7 55.3 44.3 18.0 6.1 27.0 4.1
dose * ns ** * * *** ns ** ns ** ***
crop ** ns ns *** ns ns * ns ns ns
profile *** ns ns ** *** *** ns ns ** . ***
dose : crop ns ns ns ns ns ns * ns ns ns
dose: profile ns ns ns * ns ** ns ns ns ns ***
crop : profile * ns ns ns ns ns ns ns ns ns
dose : crop :
profile ns ns ns ns ns ns ns ns ns ns ns

with the slag application, possibly due to the
competition of bivalent cations on the soil
exchange sites, which mobilised sorbed K.
As V was added with the slag, the highest
amount of slag application produced higher
losses of V in the drainage water.
Results of the soil analyses are listed in
Table 8. While all parameters were affected
by one or more experimental factors, avail-
able P (Polsen ) was not affected by any of
them.
The exchangeable cations content (Cae ,
Mge , Ke , Nae ) significantly differed, depend-
ing on the treatments. Concerning Nae this
is due to the saline irrigation water. Sodium
concentration in slag is very low, but it is
added in the water solution as NaCl. For
Cae and Ke there was a clear effect of slag
application, with a higher Cae content in D2
treatment due to slag supply and a lower
Ke content for the same treatment. This re-
sult support the hypothesis of the competi-
tion for the sorption sites of bivalent cations
(Ca in particular) on monovalent K, con-
sistently with what observed on drainage
water. The slag addition did not affect Nae
and the estimated ESP did not show a sig-
nificant decrease in D1 and D2 compared to
D0 (see Tab. 8), but only between lysimeters
treated with saline water and the control (C).
As for drainage waters, Cr (VI) was always
below the detection limit (0.2 mg/kg).
The effect of crop on exchangeable
cations was not significant, except for Mge ,
which is lower in the lysimeters planted with
potato. Results of drainage water showed
that tomato lysimeters leached more Mg.
This could be due to the higher capacity
of potato to take more of this cation than
tomato. The crop factor did not affect other
cations. This is maybe due to the large
amount provided by saline irrigation (Na),
slag application (Ca) and fertilization (K).
Significant differences were detected in
Mge , Ke , and Nae , according to the soil layer.
Especially Nae had high leaching from the
upper layer. This is consistent with the re-
sults achieved for the leachate. As Na is a
monovalent cation with a small ionic radius,
it is highly mobile in the soil. Consequently
165
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)
ESP of the first layer attained a value of
2.8%, which is similar to the value before
salt addition of 1.3%. The ESP of the lower
layer was still around 10%. The Na addition
through the irrigation led to the enrichment
of the leachable pool and then it was gradu-
ally removed by the rainfall in early autumn.
A similar pattern can be observed for Cl.
For Nae the dose/profile interaction was
also significant. The Na content in the con-
trol lysimeters (C) is similar in the two pro-
files and is also similar to the initial con-
tent of the soil before any addition (around
20 mg/kg), while in the lysimeters treated
with salts the two profiles showed very dif-
ferent Nae contents.
The concentration of Mge and Ke was
higher in the upper profile. As K was added
as potassium-sulphate and mixed in the top-
soil, this could have produced a residual fer-
tilization effect at the end of the growing sea-
son. Magnesium enrichment is possible due
to the different root uptake. The interaction
crop x profile is significant for Mge , with a
more pronounced difference between upper
and lower profile for the tomato lysimeters.
The interaction crop/dose is also signifi-
cant: the higher the slag dose the more pro-
nounced is the depletion of Mge in the potato
lysimeters, while this is not true for tomato
lysimeters.
Trace metals showed different behaviors.
Vanadium was significantly higher in the D2
lysimeters while Cr was not. The crop fac-
tor was significant for Cr but not for V. The
lower soil content of Cr in the potato-planted
lysimeters is consistent with what was ob-
served in drainage water (lower content of
Cr in the drainage of potato) and with the
hypothesis of a higher uptake of this crop.
Also the interaction dose x crop is signifi-
cant, highlighting a strong difference in the
response of the two crops to trace metals
added with the slag.
In crop production, orthogonal contrasts
highlighted significant differences with re-
gard to berries dry weight (g/plant) when the
control was compared with saline condition.
The slag treatments did not produce any ef-
fect. No significant differences were detected
for roots and stems leaves production. To-
tal biomass per plant showed differences
166
between control and saline condition (data
not shown).
Statistics did not show any significant
differences among treatments with regard
to tubers production in potato, as well as
stems and leaves biomass and total pro-
duced biomass.
6 Conclusions
The German long-term field trials with BOF
or basic slag in comparison to reference lim-
ing materials or fertilisers showed that the
annual application of slag rates meeting the
demands did not impair yields of grassland
or arable crops, but resulted in the highest
yields and crop or fodder qualities. The re-
sults of first soil and crop analyses did not
give any indication of negative impacts on
soil fertility by long-term application of BOF
slag, although significant increases of Cr and
V contents in the soil can be detected. Further
investigations will help explain the bonding
and its changes of these elements in the soil.
According to the first results of the Ital-
ian trial, it can be concluded that potato gen-
erally uptook more cations (including trace
metals) than tomato. This preliminary con-
clusion has to be confirmed by the mass bal-
ances (after the remaining drainage samples
will be analyzed) and with analyses of plant
tissues.
The analyses on drainage waters showed
significantly higher losses of V for the
lysimeters treated with the higher dose
(7 g/kg) of slags.
The results suggest that although the slag
application improved the exchangeable Ca
in the soil, it did not counteract the effect
of Na addition (sodicity) in the short term
(i.e. only one application). No effect on crop
yields related to slag addiction were ob-
served. In addiction the added Ca competed
with K for soil sorption sites resulting in des-
orption and leaching of K with higher slag
doses.
Acknowledgements
The work described in the present paper has been
developed within the project entitled "Impact of
long-term application of blast furnace and steel
slags as liming materials on soil fertility, crop
 T. Annunziata Branca et al.: Metall. Res. Technol. 111, 155–167 (2014)
yields and plant health" (Contract No. RFSR-CT-
2011-00037) that has received funding from the
Research Fund for Coal and Steel of the Euro-
pean Union. The sole responsibility of the issues
treated in the present paper lies with the authors;
the Commission is not responsible for any use
that may be made of the information contained
therein.
References
[1] J. Geiseler, Waste management 16 (1996) 59-63
[2] D. Evans, T. Hartwell, et al., Ironmaking steel-
making 31 (2004) 435-438
[3] www.worldsteel.org
[4] T.A. Branca, V. Colla, “Possible Uses
of Steelmaking Slag in Agriculture: An
Overview”, in “Material Recycling – Trends
and Perspectives”, (ed. InTech), 2012,
Dimitris S. Achilias (Ed.), ISBN: 978-953-51-
0327-1, InTech, DOI: 10.5772/31804
[5] E.U. Commission (2008). Directive
2008/98/EC of the European Parliament
and of the Council of 19 November 2008
on waste and repealing certain directives
(Waste framework directive, R1 formula
in footnote of attachment II) http://eur-lex.
europa.eu/LexUriServ.LexUriServ.do
[6] Euroslag (2006) Legal Status of Slags.
Position Paper. January 2006. The European
Slag Association – EUROSLAG. Duisburg,
Germany
[7] Euroslag (2012), Position Paper on the status
of Ferrous slag complying with the Waste
Framework Directive (Article5/6) and the
REACH Regulation, April 2012
View publication stats
[8] E.C. Regulation (2006). “No. 1907/2006
of the European Parliament and of the
Council of 18 December 2006 concerning the
Registration, Evaluation, Authorisation and
Restriction of Chemicals (REACH)”. eur-lex.
euroDa. eu/LexUriServ/LexUriServ.do
[9] M. Kühn, H. Spiegel, F.A. Lopez, M. Rex, R.
Erdmann, EUR(22033): (2006) 1-152
[10] H. Motz, J. Geiseler, Waste Management 21
(2001) 285-293
[11] C. Pistocchi, G. Ragaglini, T.A. Branca, E.
Bonari, V. Colla, “Use of BOF steel slag in
agriculture: column test evaluation of ef-
fects on alkaline soils and drainage wa-
ter”, Proceeding of The 7th Conference on
Sustainable Development of Energy, Water
and Environment Systems, July 1-7, 2012,
Ohirid, Republic of Macedonia
[12] X. Wang, Q-S. Cai, Pedosphere 16 (2006) 519-
524
[13] M. Rex, “Ecological impact assessment of
40 years of different fertilising measures
on the grassland vegetation of a meadow
in the Middle Black Forest”. VDLUFA-
Schriftenreihe 40 – Kongreßband 1995,
pp. 639-642
[14] M. Rex, “Yields and botanical developments
of permanent grassland in the Middle Black
Forest as an effect of long-term mineral fer-
tilisation” published in: Felix-Henningsen,
P. und Wegener, H.-R. (Hrsg.): Boden und
Landschaft. Schriftenreihe zur Bodenkunde,
Landeskultur und Landschaftsökologie,
Band 17 (1997) 77-90
[15] N. Mott, “The implementation of fodder
value numerals at the assessments of grass-
lands”, Das Grünland 7 (1957) 1-4
167