1 Introduction

Utilization of non-animal wastes as soil amendments is

common in order to improve soil fertility and productivity
(Rechcigl, 1995). In addition to sewage sludge and compost
some industrial byproducts such as fly ash, blast furnace
slag, phosphogypsum, paper-mill sludge, and paper de-
inking sludge are used. Paper de-inking sludge, is created
during the processing of paper for recycling. In order to
avoid landfilling and incineration of the sludge, the use by
soil application has increased in some countries. Several
studies were performed with paper de-inking sludge and its
effects on soils and vegetation. They have shown numerous
benefits on plant growth, crop yield, and soil physical,
chemical, and biological properties (Chantigny et al., 2000;
Chantigny et al., 1999; Fierro et al., 1999; Simard et al.,
1998; Cabral and Vasconcelos, 1993). Adverse effects have
been limited to deficiencies in nitrogen and phosphorus
(Fierro et al., 1997).
The term iron blue pigments is nowadays used for a number
of older names, e.g. Paris blue, Prussian blue, Berlin blue,
Milori blue, and others (Buxbaum, 1998). These blue
pigments have the general formula A
I
Fe
III
Fe
II
(CN)
6
where
A represents Na
+
, K
+
, or NH
4
+
. Iron blue pigments are very
important in the printing industry for the production of blue
J. Plant Nutr. Soil Sci. (2001), 164, 637641 (2001) WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001 1436-8730/01/0612-0637 $17.50+.50/0
Cyanide in paper de-inking sludge used as a soil amendment
Tim Mansfeldt
1*
1
Arbeitsgruppe Bodenkunde und Bodenkologie, Fakultt fr Geowissenschaften, Ruhr-Universitt Bochum,
D-44780 Bochum, Germany
Accepted 12 September 2001
Summary Zusammenfassung
Paper de-inking sludge is processed during the recycling of paper,
and is sometimes used as a soil amendment. In this study the effect
of a compost application on the cyanide (CN) status in soils of a
public park was investigated. The compost was a mixture of
chipped limbs and paper de-inking sludge. Furthermore, the
cyanide solubility was studied by conducting batch experiments
with different pH levels. Total cyanide in the amended soils ranged
from 540 to 740 mg CN kg
1
, and water soluble cyanide from 170
to 370 mg CN l
1
as determined by means of an aqueous extract.
Easily-liberatable cyanides, which include the toxic free cyanide
(HCN and CN

) and weak metal-cyanide complexes, were not

present in the soil. From this result and the fact that iron blue
pigments are used during paper printing, it can be inferred that
cyanides occurring here were exclusively stable iron-cyanide
complexes [Fe(CN)
6
]. With increasing pH the solubility of cyanide
increased. In contrast to soils of coking plants, in which cyanide
occur as Berlin blue, Fe
4
[Fe(CN)
6
]
3
, the cyanide solubility in the
paper de-inking sludge amended soils was substantially lower,
especially in the neutral and alkaline range. Thus, cyanides in paper
de-inking sludge could be present as sparingly soluble metal-
cyanide compounds with the general formula A
2
B[Fe
II
(CN)
6
] with
A = K
+
, Na
+
and B = Ca
2+
or divalent transition metals and
B
2
[Fe
II
(CN)
6
] with B = divalent transition metals. Pollution
exposure by the pathways soil ? human, and soil ? air ?
human can be neglected. However, since leaching of iron-cyanide
complexes into the ground water cannot be excluded, and since
they are decomposed to HCN when exposed to day light,
environmental hazards by the pathway soil ? ground water ?
surface water are possible. This is the risk arising from paper de-
inking sludge applications to soils.
Key words: cyanide / paper de-inking sludge / pH / soil
amendment / soil contamination / solubility
Cyanid im als Bodenverbesserungsmittel
eingesetzten Papier-Deinkingschlamm
Papier-Deinkingschlamm ist ein Rckstand der Altpapierauf-
bereitung und wird manchmal als Bodenverbesserungsmittel einge-
setzt. In dieser Arbeit wurde der Einfluss einer Kompostapplikation
auf den Cyanid-Status in Bden eines ffentlichen Parks untersucht.
Der Kompost war eine Mischung aus Rindenmulch und Papier-
Deinkingschlamm. Weiterhin wurde die Cyanid-Lslichkeit in
Schttelversuchen bei unterschiedlichen pH-Werten getestet. Die
Gesamtcyanidgehalte in den behandelten Bden reichten von 540
bis 740 mg CN kg
1
, und die der gelsten Gesamtcyanid-Konzen-
trationen im wssrigen Extrakt von 170 bis 370 mg CN l
1
. Leicht
freisetzbare Cyanide, welche die toxischen freien Cyanide (HCN
und CN

) und schwachen Metallcyankomplexe umfassen, konnten

nicht nachgewiesen werden. Aus diesem Ergebnis und der
Tatsache, dass whrend des Papierdrucks Eisenblau-Pigmente
verwendet werden, kann gefolgert werden, dass die Cyanide
ausschlielich als stabile Eisencyankomplexe, [Fe(CN)
6
], vorlagen.
Mit steigendem pH nahm die Lslichkeit der Cyanide zu. Im
Gegensatz zu Kokereibden, die mit Berliner Blau, Fe
4
[Fe(CN)
6
]
3
,
belastetet sind, war die Cyanid-Lslichkeit in diesen Bden
wesentlich geringer, besonders im neutralen bis alkalischem
Bereich. Cyanide im Papier-Deinkingschlamm knnten in Form
schwer lslicher Metallcyanverbindungen mit der allgemeinen
Formel A
2
B[Fe
II
(CN)
6
] mit A = K
+
, Na
+
und B = Ca
2+
oder ein
zweiwertiges bergangsmetall und B
2
[Fe
II
(CN)
6
] mit B = ein
zweiwertiges bergangsmetall vorliegen. Gefhrdungen ber den
Pfad Boden ? Mensch und Boden ? Luft ? Mensch knnen
ausgeschlossen werden. Da aber ein Eintrag von Eisencyankom-
plexen in das Grundwasser mglich ist und diese im Tageslicht
Blausure freisetzen, ist eine Umweltgefhrdung ber den Pfad
Boden ? Grundwasser ? Oberflchenwasser denkbar. Hierin liegt
ein Risiko in der Anwendung von Papier-Deinkingschlamm als
Bodenverbesserungsmittel.
* Correspondence: Dr. T. Mansfeldt; E-mail: tim.mansfeldt@ruhr-uni-
bochum.de
637
copying paper and blue paper. De-inking sludge is composed
of wood fibre, fillers, ink, and the chemicals used to
dissociate these materials from the pulp fibre. Since iron
blue pigments are cyanide-bearing complex compounds, any
paper de-inking sludge may contain cyanide. Cyanides are
thus added to the soil when using paper de-inking sludge as
an amendment. Cyanide is a hazardous substance in sense of
the Bundes-Bodenschutzverordnung, BBodSchV (1999).
Some studies dealt with the effects of paper de-inking
sludge application on environmental quality (Trpanier et
al., 1998; Meyn et al., 1997; Beyer and Mueller, 1995).
However, cyanide was not a subject of concern in the
mentioned studies.
In this study the effects of paper de-inking sludge
application on both the cyanide content and forms in soils
of a public park were investigated. In addition, the solubility
of cyanide in the soils was checked as well as the effect of
pH on cyanide solubility. The main objective was to evaluate
the environmental hazards arising from cyanides, which
occur in these paper de-inking sludge amended soils.
2 Materials and methods
2.1 Site, sampling, and sample preparation
Samples were obtained in fall 1999 from a public park in Germany, which
was cultivated in 1996 by the addition of organic waste. The site was a
former mining area. The organic wastes consisted of a mixture of compost
(chipped limbs) and paper de-inking sludge. It was incorporated into the
soil by roto-tilling to a depth of about 15 cm. On three plots of 250 m
2
in
size, each 15 samples were randomly taken to a depth of about 15 cm. The
15 sub-samples (each about 0.5 kg) were manually homogenized. In total,
three composite samples were obtained. Samples were passed through a
metal sieve (2 mm) and stored in the dark at 5
o
C. Aliquots were dried at
60
o
C and ground. Water content of the samples was determined at 105
o
C,
and all results reported hereafter are expressed on a mass of oven-dry
samples.
2.2 Soil properties
Total carbon was determined by dry combustion on ground material at
1,200
o
C (TR 3600, Deltronik, Dsseldorf/Germany). The CO
2
was
absorbed in an alkaline solution and detected by Coulomb electrochemical
titration. Inorganic carbon was measured by adding HClO
4
(15 %) to the
samples, which were pre-heated to 60
o
C, using the same analyzer. Organic
carbon was calculated as the difference between total and inorganic carbon.
Total nitrogen was determined by dry combustion on ground material at
1,200
o
C and the evolved N
2
was detected by thermal conductivity (vario
EL, Elementar Analysensysteme, Hanau/Germany). The pH of the fresh
soil was measured potentiometrically in a 0.01 M CaCl
2
-suspension (10 g
soil, 25 ml solution). Total cyanide was extracted from fresh soils by means
of an alkaline extraction (Mansfeldt and Biernath, 2001a). This alkaline
extract was obtained by treatment of 10 g soil with 100 ml of 1 M NaOH
for three times. The extracts were digested under acid conditions and boiled
according to the German Standard Methods by means of a micro-
distillation technique (Mansfeldt and Biernath, 2000). Additionally, easily-
liberatable cyanide was determined according to the German Standard
Method (DEV, 1988). This digestion was performed at pH 4 and room
temperature for four hours with a micro-distillation technique and a
modified digestion vessel on fresh material using a weight-in of 1 g
(Mansfeldt and Biernath, 2001b). Easily-liberatable cyanide consists of the
so-called free cyanide, hydrogen cyanide (HCN) and cyanide ion (CN

),
and weak metal cyanide complexes, i. d. those with copper, zinc, and
nickel, for example [Zn(CN)
4
]
2-
. In all cases, the HCN evolved was
absorbed in an alkaline solution and the cyanide ion was determined
spectrophotometrically at 600 nm using a barbituric acid-pyridine solution
(Mansfeldt and Biernath, 2000). General information about the samples is
given in Tab. 1.
2.3 Aqueous extract
An aqueous extract was obtained by adding 500 ml demineralized water
to 50 g fresh material in a 1000 ml polyethylene flask. Samples were
shaken end-over for 24 hours at 5 rpm. After extraction, a 250 ml extract
was centrifuged for 10 min at 15,300 g and vacuum-filtered through a
0.45 mm cellulose nitrate filter. The extract was analyzed for pH, total
cyanide, and easily-liberatable cyanide as mentioned above.
2.4 Cyanide solubility as influenced by pH
The effect of pH on cyanide solubility in the soils was studied by a batch
technique. Extraction was carried out by adding 100 ml 0.01 M CaCl
2
and 7
different volumes of 1 M NaOH or 1 M HCl to 40 g fresh sample (250 ml
polyethylene flask). The extract solution was filled up to 160 ml with 0.01
M CaCl
2
. Samples were shaken end-over for 3 days at 5 rpm, centrifuged
for 10 min at 15,300 g and vacuum-filtered through a 0.45 mm cellulose
nitrate filter. The extracts were analyzed for pH and total cyanide as
mentioned above. Extractions were performed in the dark.
3 Results
All soil samples were contaminated with cyanide (Tab. 2).
The mean value was 660 mg total CN kg
1
. In Germany, the
reference value laid down for cyanide-contaminated soils
Table 1: Some properties of three top soil samples (0 to 15 cm) from a
public park amended with paper de-inking sludge.
Tabelle 1: Einige Eigenschaften von drei Oberbden (0 bis 15 cm) eines
ffentlichen Parks, der mit Papier-Deinkingschlamm behandelt wurde.
parameter sample
A B C
pH (CaCl
2
) 7.0 7.2 7.4
organic carbon, g kg
1
190 191 169
total nitrogen, g kg
1
5.4 5.5 6.1
C:N 35 35 28
Table 2: Total and easily-liberatable cyanide in three soil samples and
aqueous extracts of a public park amended with paper de-inking sludge.
Values are means of three replicates ( standard deviation; n.d. not
detectable, < 1 mg CN l
1
).
Tabelle 2: Gesamtcyanid und leicht freisetzbares Cyanid in drei
Bodenproben und wssrigen Extrakten eines ffentlichen Parks, der mit
Papier-Deinkingschlamm behandelt wurde. Daten sind Mittelwerte aus drei
Wiederholungen ( Standardabweichung; nd: nicht nachweisbar, < 1 mg
CN l
1
).
sample soil aqueous extract
total CN easily-liberatable CN total CN easily-liberatable CN
[mg CN kg
1
] [mg CN kg
1
] [mg CN l
1
] [mg CN l
1
]
A 710  24 n.d. 370  40 nd
B 538  22 n.d. 300  40 nd
C 736  17 n.d. 170  20 nd
638 Mansfeldt
depends on land use. In case of a public park, the reference
value is set to 50 mg total CN kg
1
(BBodSchV, 1999). Thus
the cyanide contents of these soils were more than tenfold
higher than the reference value. Water soluble cyanide
ranged from 170 to 370 mg CN l
1
with a mean value of 290
mg CN l
1
(Tab. 2). The proportion of water soluble cyanide
on total cyanide ranged from 0.3 to 0.7 %. The BBodSchV
(1999) allows the assessment of ground water contamination
by the performance of an aqueous soil extract obtained in the
unsaturated zone. In the case of total dissolved cyanide, a
reference value of 50 mg CN l
1
is laid down (BBodSchV,
1999). This value is exceeded by factor six. Easily-
liberatable cyanides were not detected, neither in the soils
nor in the aqueous extracts. For this cyanide form, a re-
ference value is laid down for ground water at 10 mg CN l
1
(BBodSchV, 1999).
In the pH range from 6 to about 11 the relationships
between pH and dissolved cyanide concentrations are
roughly linear in soils amended with paper de-inking sludge
(Fig. 1). The slopes of the regression equations of all
samples are very similar: 0.41 for sample A; 0.35 for sample
B; 0.40 for sample C. The overall regression equation for the
pH range from 6 to 11 is
log [Fe(CN)
6
] = 0.387  0.028 pH 8.7  0.219, n = 15, r =
0.971.
The correlation coefficient r was significant at P < 0.001.
However, at pH < 6 the dissolved cyanide concentrations
were extremely low. The shaded area in Fig. 1 represents pH
dependent dissolved cyanide concentrations observed for
pure Berlin blue, Fe
4
[Fe(CN)
6
]
3
, as well as for soils from
sites of former gas work plants and coking plants (adapted
from Meeussen et al. (1990) and Mansfeldt et al. (1998)).
Compared to the results of the present study, the results of
Meeussen et al. (1990) and Mansfeldt et al. (1998) differ in
two aspects: First, cyanide concentrations were larger at any
pH; and second, the relationship between pH and cyanide
concentrations was steeper. The latter aspect was inves-
tigated by calculating the slopes as reported for the German
(Mansfeldt et al., 1998) and the Dutch soils (Meeussen et al.,
1990) restricted to their linear range. The slopes range from
0.5 to 0.6 (German soils, pH 3.0 to 6.2), and from 0.6 to 0.7
(Dutch soils, pH 4.8 to 7.8). These slopes are significantly
larger than those found here for soils amended with paper
de-inking sludge. In soils from sites of former gas work
plants and coking plants, cyanide is present mostly as the
ferric ferrocyanide Berlin blue (Mansfeldt et al., 1998). As
pointed out in Fig. 1, the solubility of cyanide in Berlin blue-
contaminated soils is higher than in soils amended with
paper de-inking sludge. Therefore, cyanide extracted from
soils amended with paper de-inking sludge could not derive
from Berlin blue.
The proportion of cyanide being dissolved at any pH
differed between soil of a former coking plant site and soil
amended with paper de-inking sludge (Fig. 2). Even at pH
ranging from 8 to 10, only 10 % of total cyanide was
dissolved in paper de-inking sludge amended soil. The
release of cyanide at pH 3 to 6 was negligible. In contrast,
virtually all cyanide was dissolved in soils from the site of a
former coke oven at pH ranging from 8 to 10, and dissolution
of cyanide species at lower pH was obvious. Therefore, the
results shown in Fig. 2 support the conclusion that cyanide in
soils amended with paper de-inking sludge cannot be present
as Berlin blue.
4 Discussion
Soil is a major pathway for human, animal and ecological
exposure to environmental contaminants, e.g. cyanide.
Figure 1: Influence of pH on cyanide concentrations in 0.01 M CaCl
2
-
extracts of three cyanide-contaminated soil samples amended with paper
de-inking sludge (sample A, O 710 mg CN kg
1
; sample B, D 538 mg CN
kg
1
; sample C, & 736 mg CN kg
1
). The shaded area represents the same
relationship in soils of former coking plant sites, gas work sites, and pure
Berlin blue, Fe
4
III
[Fe
II
(CN)
6
]
3
(Mansfeldt et al., 1998; Meeussen et al.,
1990).
Abbildung 1: Einfluss vom pH auf die Cyanid-Konzentrationen in 0,01 M
CaCl
2
-Extrakten von drei mit De-Inkingschlmmen behandelten Bden
(Probe A, O 710 mg CN kg
1
; Probe B, D 538 mg CN kg
1
; Probe C, &736
mg CN kg
1
). Der schattierte Bereich gibt dieselbe Beziehung in Bden
von ehemaligen Kokereien und Gaswerken sowie die von reinem Berliner
Blau, Fe
4
III
[Fe
II
(CN)
6
]
3
, wieder (Mansfeldt et al., 1998; Meeussen et al.,
1990).
Figure 2: Proportion of dissolved cyanide in 0.01 M CaCl
2
-extracts on
total cyanide from soils amended with paper de-inking sludge (filled bars)
and soils from a former coking plant site (hatched bars) as influenced by
pH. Mean of three samples (538 to 736 mg total CN kg
1
) with 21 pH
levels for the paper de-inking sludge amended site. Mean of three samples
(40 to 435 mg total CN kg
1
) with 45 pH levels for the former coking plant
site (Mansfeldt et al., 1998). Data were classified in 6 pH-groups.
Abbildung 2: Einfluss vom pH auf den Anteil von 0,01 M CaCl
2
-lslichem
Cyanid zum Gesamtcyanid in mit Papier-Deinkingschlamm behandelten
Bden (gefllte Balken) und in Bden eines ehemaligen Kokereistandortes
(schraffierte Balken). Mittelwert von drei Proben (538 bis 736 mg CN kg
1
)
mit 21 pH-Abstufungen bei den mit Papier-Deinkingschlamm behandelten
Bden; Mittelwert von drei Proben (40 bis 435 mg CN kg
1
) mit 45 pH-
Abstufungen bei den Bden einer ehemaligen Kokerei. Daten wurden zu 6
pH-Klassen zusammengefasst.
Cyanide in paper de-inking sludge used as a soil amendment 639
When evaluating the hazards arising from cyanide in soils,
two aspects have to be considered: First, the toxicity of
cyanide, which strongly depends on species of cyanide
present. Second, the pathways of exposure to humans, which
are (1) inhalation of volatile HCN (soil ?air ?human), (2)
ingestion and dermal contact of cyanide-containing soils
(soil ? human), and (3) ground water and surface water
exposure (soil ? ground water ? human; soil ? surface
water ? human).
Hydrogen cyanide is extremely toxic and acts very rapidly.
Thus it has a very large hazardous potential against life. The
toxicity of weak metal-cyanide complexes is lower, but high
enough to classify them as hazardous substances. They
dissociate to a significant degree, thus liberating free
cyanide. The distribution of free cyanide in aqueous systems
with respect to HCN and CN

depends on pH: HCN + H

2
O
?CN

+ H
3
O
+
(pK
a
= 9.21). From a toxicological point of
view, the toxicity level of cyanides is considered by the
analysis of easily-liberatable cyanide because this species
contains the weak metal-cyanide complexes. In the case of
paper de-inking sludge easily-liberatable cyanide could not
be detected. This is in agreement with the fact, that cyanide
present here were solely coming from iron blue pigments.
During the processing of paper, iron-cyanide complexes did
not seem to be destroyed or converted to more labile cyanide
species. Absence of free cyanide in iron-cyanide contami-
nated soils was also reported by Vandenhove et al. (2000)
and Theis et al. (1994). A public park is a sensitive area,
because soil ingestion by children may take place. When
evaluating the pathway soil ?human, there is no health risk
due to the fact, that cyanide occurs as an iron-cyanide
complex. Iron-cyanide complexes are so stable that they will
not decompose in human bodies to a lethal level (Nielsen et
al., 1990).
In contrast, dissolved iron-cyanide complexes are rapidly
destroyed by photo-degradation (photolysis), and free
cyanide is liberated (Rader et al., 1993; Meeussen et al.,
1992). At first sight, photo-degradation is only relevant at
the soil surface. However, there are no studies in which the
degassing of HCN from contaminated soil surfaces was
measured. Shifrin et al. (1996) stated from a simple
modeling analysis, based on very conservative assumptions,
that the HCN evolved from a contaminated gas work site
(1,800 mg CN kg
1
) would be diluted quickly and dispersed
in air to non-toxic levels. In the present study, cyanide
concentrations were lower and cyanide solubility was very
low. Therefore, results obtained by Shifrin et al. (1996) can
be applied to this site, and the exposure pathway soil ?air
? human can be neglected.
Iron-cyanide complexes are retained or consumed in soils
by different mechanisms including precipitation, surface
precipitation, inner-sphere and outer-sphere surface com-
plexation, and chemical or microbial decomposition (Ren-
nert and Mansfeldt, 2001; Cheng and Huang, 1996; Meeus-
sen et al., 1994; Meeussen et al., 1992; Theis and West,
1986). Rates of chemical decomposition of iron-cyanide
complexes to free cyanide in soils have very slow dissocia-
tion kinetics (Meeussen et al., 1992). Microbial degradation
of iron-cyanide complexes in soils is possible, but is gene-
rally slow (Kjeldsen, 1999). Thus, decomposition is not
effective in protecting the ground water against cyanide
pollution. Precipitation of Berlin blue is restricted to extrem-
ely acid conditions, because Fe
III
-ions are needed for pre-
cipitation. Due to the first hydrolysis constant of the ferric
ion (pK
H1
= 2.19), it will precipitate as iron-(hydr)oxides
under higher pH levels. If pH rises, Berlin blue is dissolved
by simultaneous precipitation of iron(hydr)oxides. During
the processing of paper, some Fe
III
may be replaced by Na
+
,
K
+
, Ca
2+
, and divalent transition metals. Complexed cyanide
with mixtures of alkali-metals, earth-alkali metals and
transition metals or transition metals solely are sparingly
soluble (Klenk et al., 1987; Bellomo, 1970). In contrast to
Berlin blue, these iron cyanide compounds are not com-
pletely dissolved under alkaline conditions, since the first
hydrolysis constant of the accompanying cations is much
larger than those of the ferric ion. For example, the cyanide-
containing compound potassium zinc hexacyanoferrate(II)
nonahydrate, K
2
Zn
3
[Fe(CN)
6
]
2
9H
2
O, which recently was
identified in deposited blast furnace sludge (Mansfeldt and
Dohrmann, 2001), is only dissolved under extremely alka-
line conditions (Mansfeldt and Biernath, 2001a). The first
hydrolysis constant of Zn
2+
is pK
H1
= 8.96. Solubility of
cyanide in paper de-inking sludge amended soils depends on
pH and increases with increasing pH. Compared to soils
contaminated by Berlin blue, the solubility of cyanide in the
neutral and slightly alkaline range was relatively low. From
this it can be inferred that the cyanides present in paper de-
inking sludge were in the form of A
2
B[Fe
II
(CN)
6
] with A =
K
+
, Na
+
and B = Ca
2+
or divalent transition metals, and
B
2
[Fe
II
(CN)
6
] with B = divalent transition metals. Never-
theless, some cyanide will be dissolved in water as can be
concluded from the aqueous extracts. Thus, leaching of iron-
cyanide into the ground water cannot be excluded. Dissolved
iron-cyanide complexes have a large negative charge, [Fe
II/
III
(CN)
6
]
4-/3-
. The sorption of them depends on pH and
important sorbents are sesquioxides (Rennert and Mansfeldt,
2001; Cheng and Huang, 1996; Theis and West, 1986).
Ferrocyanide, [Fe
II
(CN)
6
]
4-
, is sorbed stronger on goethite
than ferricyanide, [Fe
III
(CN)
6
]
3-
, and sulfate (Rennert and
Mansfeldt, 2001, 2002). Acid soils high in sesquioxides
should retain some iron-cyanide complexes, especially
ferrocyanide. However, in substrates higher in pH, e. g.
subsoils and aquifer material, and with a sandy texture, iron-
cyanide complexes should be relatively mobile. This was
shown by Ghosh et al. (1999) for sandy aquifer material. If
leached out from contaminated sites and transported to
surface waters, these complexes are rapidly decomposed by
photo-degradation thus liberating free cyanide. The pathway
soil ?ground water ?human and soil ?surface water ?
human should be critically seen in that case.
5 Conclusions
The application of paper de-inking sludge to soils is
problematic, because these sludges contain cyanide due to
the overall use of iron blue pigments in the printing industry.
However, from a toxicological point of view acute hazards
originating from cyanide-bearing paper de-inking sludge can
640 Mansfeldt
be neglected, since cyanide is in the form of nontoxic iron-
cyanide complexes. As the solubility of the cyanide
compounds occurring in paper de-inking sludge strongly
depends on pH, both environmental assessment and
monitoring of cyanide in such soils should consider soil
pH and the content of sesquioxides, which act as sorbents.
Under acid conditions the solubility of cyanide is low.
However, if the soil pH is consistently above pH 7 to 8, the
solubility of iron-cyanide complexes is favored and in the
long term some inputs of iron-cyanide complexes into
ground water cannot be excluded. In addition, the dis-
solution kinetics of cyanide compounds in paper de-inking
sludge amended soils, which were not investigated here,
should be important for soil solution concentrations of
cyanide and for the assessment of ground water pollution by
cyanide.
Acknowledgments
For technical assistance I am grateful to Heidi Biernath, Ruhr-University
Bochum.
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