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ScienceoftheTotalEnvironment627 (2018) 1167-1173

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On the volatilisation and decomposition of cyanide contaminations from


gold mining
Andreas Bruger a'*, Gunter Fafileka, Oscar J. Restrepo B.b, Lucas Rojas-Mendoza b

a
Institute ofChemical Technologies andAnalytics, Vienna University ofTechnology, Getreidemarkt9, A-1060 Vienna, Austria b Departamento de Materialesy Minerales, Facultad de Minas,
Universidad Nacional de Colombia, Medellin, Colombia

H I G H L I G H T G R A P H I C A L A B S T R A C T
S
• After volatilisation from water, no cyanide
AIR
destruction via photolysis or oxidation LHCN(a) + Vz Oj —» HCNO(g) (lifetime: 6 months - 5 years) HCN(g) ^ H(2s) + CN(2n) (hv< 200 nm)
was observed.
• High concentrations of cyanide were
UUU
found in water bodies downstream gold s
processing centres.
• A mass balance ofcyanide over the com-
plete cyanidation process is necessary.
• A simple and location-independent
method for cyanide analysis is applied.
heap-leaching

,0
recyding/destruction
^
v> recovery of gold tailings pond
dilution/discharge
lx
Me + Cyanide ox> Me-Cyanide(al
SOIL/WATER

A R T I C L E I N F O A B S T R A C T

Article history: Cyanide leaching is the predominant process of gold extraction in large scale mining. Current initiatives for reducing
Received 13 November 2017 Received in the use of mercury in small scale and artisanal mining tend towards the cyanide technology as the only feasible
revised form 30 January 2018 Accepted 30 alternative. Thus, the deliberate handling in consideration of the hazardous nature of cyanide compounds is an
January 2018 Available online xxxx issue of particular importance. The hydrogen cyanide volatilised during the leaching process and from the tailings
solutions after the gold extraction is reported to be destroyed by oxidation and photolysis from the surrounding
Editor: F.M. Tack
atmosphere of gold mines and the sunlight. Cyanide solutions, drained into the surrounding waterbodies are stated
to volatilise at a high rate, thus detoxifying them and releasing hydrogen cyanide to the air. In this study laboratory
Keywords: experiments and field tests were conducted to deliver basic data for the volatilisation and destruction of cyanide in
Cyanide the environment.
Oxidation In our laboratory tests we observed neither oxidation by the oxygen of air nor photolysis by UV-irradiation of cy-
Photolysis anides after volatilisation from water. The whole amount of volatilised cyanide was found in the exhaust gas after
Artisanal gold mining absorption in a strong basic solution.
Field experiments in Segovia (Colombia) could confirm these findings. Cyanide concentrations in a range 17 to 30
mg/L were measured in a local creek. Hydrogen cyanide amounts of 5 ppm were found in the atmosphere sur-
rounding cyanide leaching facilities. With the findings of this study we want to point out that the concentrations of
cyanide in the surrounding of cyanide leaching facilities exceed uncritical limits and a destruction via oxidation and
photolysis is not detectable. These conclusions should result in initiatives to protect workers and the surrounding
population of gold mines from contaminations of cyanide treatments.
© 2018 Elsevier B.V. All rights reserved.

* Corresponding author.
E-mail addresses: andreas.brueger@tuwien.ac.at (A. Bruger), guenter.fafilek@tuwien.ac.at (G. Fafilek), ojrestre@unal.edu.co (O.J. Restrepo B.).

https://doi.org/10.1016/j.scitotenv.2018.01.320 0048-
9697/© 2018 Elsevier B.V. All rights reserved.
1168 A. Bruger et al. /Science ofthe Total Environment627 (2018) 1167-H73

1. Introduction was calculated based on effects of nitroprusside on humans (Schulz et al.,


1982). Both publications can hardly match the requirements for a
About 90% of the world's gold mining workforce is represented by contemporary toxicological estimation. A main problem in the collection of
artisanal and small-scale gold miners, producing around 15% of the world's information concerning the toxicity of cyanide to humans is the insufficient
gold (UNEP, 2012). In Colombia there are about 200,000 artisanal gold comparability of literature data. The increasing knowledge about cyanide
miners, using mainly mercury for the gold processing (Cordy et al., 2011). poisoning restrains the necessity to revise the findings from the mainly prior
The amalgamation process suffers a low capability of mercury recovering. research with its different state of knowledge and methods. Approaches in
Rarely >30% of the gold is captured (UNEP, other locations of possible cyanide contaminations suggest further in-
2012) . The Hg-contaminated tailings are further leached with cyanide, vestigations of health effects as a result of cyanide leaching (Akinrele, 1986;
followed by zinc shaving precipitation. After the leaching process, the gold- Dhas etal., 2011; Kumbnani etal., 1990).
barren waste, containing metallic mercury and mercuric cyanide complexes A second claim is that cyanide is naturally degraded and does not
as well as other toxic metal complexes with cyanide is discharged into local persist in the environment due to oxidation and photolysis in the atmosphere
creeks. This two-stage process of whole-ore amalgamation followed by (Logsdon et al., 1999; TRI, 1998). The USEPA describes ‘natural
cyanidation is practiced in artisanal gold mines around the world degradation’ as a general term for all of the processes that may reduce the
((Krisnayanti et al., 2012; Shandro et al., 2009; Telmer and Veiga, 2009). total cyanide concentration in waste (in solution and soil) including
Initiatives were launched in recent years to reducing mercury in artisanal volatilisation and evolution of HCN from CN-, (USEPA, 1994). This can be a
and small-scale gold mining (e.g. the Global Mercury Project (UNIDO, 2004) slightly misleading description as the chemical understanding of
and the Minamata Convention on Mercury (UNEP, ‘degradation’ seems to tend towards decomposition in this context (IUPAC,
2013) ). Cyanide is recommended as a viable alternative in small scale 2000; Rubo et al., 2000). Because of these varying definitions in literature,
mining (UNEP, 2012). the persistence capability of cyanide in the environment should be followed
The utilisation of cyanide leaching processes in artisanal mining requires in atmosphere, water and soil:
the formation of mining cooperatives or associations to the extent that the The lifetime of hydrogen cyanide in the troposphere is calculated as 5
gold ore processing, using cyanide, can hardly be done by individuals. In years primarily caused by oxidation and 6 months if influenced by ocean
combination with technically advised processing centres and the appropriate uptake; photolysis is described as being negligible due to the fact that the
working with cyanide, this would furthermore support projects to reducing strong H-CN bond cannot be broken by photons available in the troposphere
mercury in artisanal mining. Approach has been taken to support the (Cicerone and Zellner, 1983; Kleinbohl et al., 2006). Experiments including
collaboration between large and small-scale miners (IFC- the persistence of cyanide in water are published with varying results.
CommDev/CASM/ICMM, 2008). In large-scale mining, cyanide leaching is Significant oxidation of cyanide with UVA irradiation in synthetic wastewater
the predominant method for the gold extraction. It is reported to be utilized in is found by Ozcan et al. (2012), whereas Simovic (1984) showed that neither
90% of gold producing operations worldwide (Laitos, 2013; Mudder and the effects of UV light nor oxidation significantly contribute to the removal of
Botz, 2004). cyanide in NaCN solutions.
Concerning the use of NaCN for the leaching process, an estimate for Free cyanide is reported to have potentially high mobility in soil and
the release to the atmosphere of 30%-50% as HCN and a global use of groundwater environments, depending on factors like pH, humidity and the
330.0 t of NaCN for gold mining per annum is quoted by NICNAS type of soil, resulting in diffusion up through the soil and release to the
(2010), this leads to 55,000 to 90,0001 HCN. Compared to the global at- atmosphere (Kjeldsen, 1999; NICNAS, 2010). Cyanide-metal complexes can
mospheric budget for HCN of 2 mio t this would be a minor contribution to be enriched in soils and represent a potential hazard to the groundwater in
the global HCN release (NICNAS, 2010). Considering more recent data for releasing toxic metal compounds and free cyanide as a result of
the usage of NaCN in the gold extraction of 710,000 t, based on decomposition under different circumstances (Kjeldsen, 1999; Shehong et
880.0 t world production in 2013 (Mcgroup, 2014) with 81% of this al., 2005).
demand used for gold extraction (Kobayashi, 2012) and the global trend of The requirement of further investigations concerning the influence of
increasing cyanide consumption with decreasing ore grade (Mudd, 2007), sunlight, oxidation and volatilisation on cyanide removal in water and air is
the contribution is doubled. part of the motivation for this work. The results of these investigations could
Cyanide-leaching accidents in the past have received widespread public help to estimate the contamination of the atmosphere surrounding leaching
attention. The costs of remedial actions after acid mine drainage and facilities. Available data range from <1 ppm HCN at distances >1 m from the
leakages of the Summitville mine (USA) exceeded the total profit of gold and heaps (DeVries, 1996) to values of 0.36 ppm CN in air depending on
silver extraction (CDPH, 2010; Ketellapper et al., 1996). The discussion distance (in a range 2-52 m) to the leach pad and the wind conditions
following the cyanide spill at Baia Mare in Romania when a tailings dam (Feigley et al., 1984). In air screenings as a consequence of the ICMC, the
broke in 2000 resulted in the development of the International Cyanide 2011 report of the Yanacocha mine (Peru) indicates areas with hydrogen
Management Code (ICMC) of best practice for the use of cyanide in the cyanide levels in excess of 10 ppm (Golder, 2011). The TWA (maximum
production of gold. This program was designed by a multi-stakeholder average airborne concentration to which workers may be exposed without
steering committee under the guidance of the United Nations Environmental adverse effect over an eight - hour working day, for a five - day working
Program (UNEP) and the International Council on Metals and the week) is 0.9 ppm, following the recommendations for Indicative occupational
Environment (ICMI, 2009). The ICMC is a voluntary program for gold mining exposure limit values (SCOEL, 2010), published by the European
companies as well as for cyanide producers and transporters. It is Commission.
considered as an initiative to lift international standards as well (NICNAS, Based on comprehensive data of cyanide exposure in any processing
2010). The ICMC as well as the new international guidelines and limits seem step and every place of possible contamination from gold mines and
to represent a major step forward to improving social, health, safety and processing plants, an assessment of the hazard potential for different lo-
environmental conditions in the gold mining sector. However, despite these cations can be done to minimize the pollutions, caused by cyanide com-
improvements, the risk of possible accidents and fatalities remain (Newmont, pounds. A mass balance as a result of this comprehensive data could help
2010; Husseini, 2013; T-SG, 2014). the comparison of cyanide exposures in different gold mines. In this work,
In literature there is some claim that small non-lethal doses of cyanide one step forward is taken in receiving more information concerning the
do not give rise to chronic health problems (Logsdon et al., 1999), or quickly volatilisation and degradation of cyanide in water and air. Experiments were
metabolize in the body arguing the uncommonness of chronic exposure to done in the laboratory and as a consequence in field studies in Segovia in
cyanides (SWA, 2013). Two detoxification rates have been estimated for the Department of Antioquia, Columbia. In Segovia, the largest gold
men after intravenous injection (e.g. SCOEL, 2010; USEPA, 2010). The rate producing town in Antioquia, artisanal as well as large scale mining activities
of 17 pg/kg/min is based on a study using hydrocyanic acid in saline are found (Garcia et al., 2015). The mining area of Segovia in Colombia is
solutions (Loevenhart et al., 1918), the metabolisation data of 1 pg/kg/min difficult to access and although mining has been carried out for many years,
A. Bruger et al. / Science of the Total Environment 627 (2018) 1167-1173 1169

the working conditions are less than ideal. There are difficulties of access, nm at a distance of 4 cm. Relative intensities of light emitted by the tubes as
supplies and public order, which makes the measurement and control of the a function of wavelength were measured with an ocean optics fibre optic
processes difficult, therefore, it is common for discharges and sometimes spectrometer, calibrated against a white light source of known colour
environmental damage to the soils and water sources ((Bustamante et al., temperature. The comparison to the solar irra- diance (direct + circumsolar
2016). This situation also influenced the possibilities of collecting samples light AM1,5, ASTM G-173 with an irradi- ance of 24 W/m2 between 320 and
and thus limited the number of possible measurements in the field 390 nm) is shown in Fig. S 1 in the supplementary information.
experiments. The UV irradiation in our experiments was done, using three fluorescent
bulbs placed in a box with a reflecting background. The light source was
2. Materials and methods placed in a distance of 1.5 cm to the reaction flask, measured between the
edge of the bulbs and the outer surface of the flask. The radiation loss
2.1. Laboratory setup through the glass of the flask is approximately 15% in the used wavelength
range and can be followed in the supplementary information (Fig. S 1). The
The determination of free cyanide was based on a standard method for setup for the photolysis-experiments was similar to the volatilisation
the collection of HCN gas and the measurement of CN-concentra- tions in experiments described above. Buffered cyanide solutions (pH = 10.3, initial
solution (SMWW, 2012). According to the standard method the volatilised cyanide concentration: 400 mg/L) were filled into the reaction flask and
HCN in the reaction flask was collected via suction of laboratory air through irradiated between 24 h and 72 h. Air suction was done with a flow rate of 13
the volatilisation flask using a vacuum pump as an aspirator. Volatilisation L/h. The CN concentration in the reaction flask and in the absorption flask
tests at high pH (between 13 and 14) resulted in an increase of the cyanide was analysed after the experiments to determine the cyanide loss due to
concentration in the flask due to water volatilisation. Experiments in an initial photolysis.
pH range of 12.6 to 13 (with NaOH) were accompanied by a significant
decrease in pH due to CO absorption from the laboratory air. An initial pH
2 22. Setup for the field measurements
13 solution, decreased to pH 11 after 96 h at an airflow rate of 12 L/h;
volatilisation of water in this solution was up to 4% in 24 h depending Investigations of the cyanide content in the air surrounding processing
predominantly on the relative humidity of the atmosphere surrounding the plants were done at three locations. At the Entable JM, cyanide in air was
experiment. According to the standard method, the pH of the absorption measured in a distance of 1 m to a vat during a cyanide leaching process,
solution for the collection of HCN is 12.6. Preliminary tests in our laboratory activating the slurry with gas introduction. In the second location, the Mina
showed that KCN in a CN-concentration of400 mg/L was stable against La Campana, measurements were done inside a tank for the storage of
volatilisation only in NaOH solutions of pH ≥ 14 (see results). To overcome cyanide solution before usage, in a distance of 1 m to the cyanide solution.
the above described problems, the standard method was modified as The same distance was followed in the third location, the Mina Cogote,
follows: where the leaching was done in a tank equipped with an agitator and with
Carbonation and evaporation of water were minimised by adding a 250 gas introduction.
mL absorption flask, containing 200 mLofa 1 M NaOH solution preceding the The method for the field investigations was similar to the method
flask containing the cyanide solution. The laboratory air was bubbled through described in the laboratory volatilisation experiments, but was adapted for a
a medium-porosity frit in this absorption flask for the removal of CO2 and the simple location-independent application. The measurements were done in a
humidification of the laboratory air. After the implementation of the additional distance of 1 m to the cyanide containing slurry. The influence of wind was
absorption flask, the pH didn't change over the period of the experiments excluded by choosing an absorption period with calm conditions. These
and the evaporation of water in the reaction flask was <0.2-0,3% per day. were done using a stand-alone setup for sample drawing (supplementary
The amount of evaporated water was determined gravimetrically and information Fig. S 2). A membrane air pump, (Zhongshan Jingdian Electric
incorporated into the calculation of the degree of cyanide volatilisation. Appliance, 0.1-0.8 L/min), was connected to a 1.2 Ah lead-acid rechargeable
The volatilisation of HCN was assessed by passing the humidified and battery (Exide Powerfit) to allow operations of about 6 h. To ensure longer
CO2-liberated laboratory air through a 500 mL three-neck round- bottom experiment durations, a 3 W/630 cm2 amorphous solar panel could be
flask, containing 200 mL of buffered cyanide solution (surface area: 78 cm - , 2
connected to the unit. The air-flow rate was controlled using a flow meter
initial cyanide concentration: 400 mg/L (15.37 mM)) without bubbling through (Fischer & Porter). pH measurements were done with universal indicator
the solution. The buffered solutions were produced, following standard strips. The whole equipment was designed for a simple transportation with
preparation methods (Bates and Bower, 1956). The chosen basic range of durable materials and varying applications, considering the different archi-
the reaction solutions (pH 9-pH 14) should cover the whole range of possible tecture of the goldmines in this region sometimes difficult to access.
pH values found during the cyanide leaching process in gold processing The sampling for the cyanide measurements in water was done at three
facilities. positions in a river flowing through the area of gold mining (Quebrada la
The HCN loaded air was bubbled through a medium-porosity frit in a Cianurada). The locations of the sampling were chosen in order to compare
250 mL absorption flask, containing 200 mL absorption solution for the different areas of potentially high cyanide levels and to make an estimation
cyanide absorption. For the absorption as well as for further processing of about the influence of contaminated side streams to the main stream of the
the CN-containing samples, 1 M NaOH solutions were used. A second river that collects most of the drains of the gold mines. One location was in a
absorption flask was appended to control the efficiency of HCN absorption tributary stream, flowing through a mining area, the second point for the
and removed, after the comprehensive absorption of cyanide in the first flask sampling was in the
was confirmed. The air suction was done using flow rates between 12 L/h
and 36 L/h (36 L/h is the maximum to keep the liquid phase in the absorption
flask). The flow rate was adjusted with a rotameter, connected to a needle
valve (Fischer & Porter). Compared to natural wind intensities, these flow
rates are rather low but the target is reached with the complete absorption of
volatilised HCN. The decrease of volume in the absorption flask due to
volatilisation of water (up to 0.1% per day) was neglected at low cyanide
absorption concentrations and incorporated in the calculations with cyanide
absorption concentrations, higher than 100 mg/L in the absorption flask. A
schematic of this set-up is shown in Fig. 1.
The light source for the UV irradiation consisted of UVA fluorescent
tubes (Sylvania Lynx BL350). This UV source has a wavelength maximum at
350 nm and a light irradiance of 66 W/m2 measured between 320 and 390
1170 A. Bruger et al. /Science ofthe Total Environment627 (2018) 1167-H73

A. Absorption flask with fritted glass diffuser for CO 2 removal and H2O saturation, pH 14
B. Reaction flask with sample solution, with optional UV-radiation
C. UV-lamp
D. Absorption flask with fritted glass diffuser for absorption of volatilised HCN, pH 14
E. Suction flask trap
F. Rotameter
G. Vacuum pump

Fig. 1. Apparatus for the determination of volatilisation and decomposition of cyanide with optional UV irradiation.

main stream before the tributary stream mouth and the third one after this this range. All samples were measured within minutes after collection. The
conflux, both in a distance of about 100 m to the tributary stream mouth (Fig. amount of photolysis and oxidation of HCN was determined in comparing the
2.). The sampling area was located downstream outside of the town. HCN loss in solution and the absorbed cyanide as a result of volatilisation. A
difference between the sum of these values and the initial concentration of
2.3. Cyanide analysis cyanide in the solution should give an argument for the degradation of HCN
as a result of oxidation, photolysis or hydrolysis to ammonia.
Analysis of the CN-content was done by titration against AgNO3 with p- In order to ensure that measuring equipment is not destroyed over the
dimethylaminobenzalrhodanine, (all reagents are Merck p.a.). Using a 10 mL period of field investigations during transportation through rough terrain, the
burette, half droplets with 0.02 mL volume could be produced during titration titration was done with 10 mL and 1 mL pipettes depending on the expected
as a minimum. The temperature in the laboratory was constant at 23.5 °C cyanide content in the samples obtained from the air experiments. As
(±0.4 °C). The influence of the temperature on the described analytical preliminary experiments showed low cyanide absorption rates in leaching
method was determined by measuring the CN content at a temperature solutions of a pilot plant at the Universidad Nacional de Colombia the
range 13 °C to 33 °C. No difference was noticed in detection limit, using a 1 mL graduated

Fig. 2. Sampling in the Quebrada la Cianurada (Location before contributing mine stream).
A. Bruger et al. / Science ofthe Total Environment 627 (2018) 1167-1173 1171

Fig. 3. Volatilisation of HCN in water at pH 9 in% of the initial concentration. Squares: measured HCN concentration m the
gas phase identified via absorption mNaOH (HCN g) asafunction of volatilisation time t Solid line: regression for 1st order
kinetic (1-exp(-t/t0)) with the time constant (to) of 7,24 s.
pipette was tested. Droplets of 0.01 mL volume could be produced on the With cyanide solutions at a constant pH of 9 over a volatilisation period
wall of the titration flask and shaken into the cyanide solution. According to of 1 h to 96 h, it can be shown that the curve in Fig. 3 exhibits first order
calculations, 1 ppm CN is equal to 1.064 mg/m3 at 30 °C. With a gas flow kinetics.
rate of 12 L/h in an absorption flask with a liquid volume of 200 mL, this In these experiments, besides the volatilisation of HCN, no further
correlates to 0.013 mL AgNO3 solution for an absorption period of 2 h and reaction was found. In each volatilisation experiment without further
0.006 mL for a duration of 1 h. For a more accurate investigation of the treatment (e.g. UV irradiation), the amount of HCN loss in the buffered
detection limit, the titrant was diluted 1:10 and mixed with cyanide-solutions solution was equal to the HCN content in the absorption flask.
with concentrations ranging 0.1 to 0.5 mg/L in further preliminary laboratory The second route was followed in investigating the HCN content in the
experiments. These tests confirmed a detection limit of 0.1 mg/L (equates to gas phase surrounding cyanide solutions in a range of pH 9 to 14. The
2 ppm with 1 h absorption time and 1 ppm with 2 h absorption time in our duration of the experiments was adapted to the extent of cyanide
experiments). For more precise data, the analysis method would have to be volatilisation from solutions over this pH range - the longest volatilisation
changed towards a more complex or location-dependent procedure. experiment was completed after 13 days. Again, the amount of HCN loss in
The analysis of samples from the river was done 4 h after sampling and the solution was equal to the volatilised HCN content in the absorption flask.
storing in glass bottles. The dark coloured bottles were completely filled with For a plot of comparable results, the half-life of HCN in the buffered solutions
the samples and stored cold (10 °C) in the dark until the analysis was done. was calculated using first order kinetics. The results are summarized in
For the examination of the stability of cyanide solutions, handled in this way, Table 1 - measurements at pH 14 didn't result in detectable HCN absorption
laboratory tests were done using cyanide solutions (40 mg/L) in tap water, from the gas phase.
kept in the same glass bottles under similar conditions. The cyanide content The plot of the HCN half-life in solution against the pH with its loga-
decreased <0.1%/h in durations up to 10 h and was consequently neglected. rithmic behavior is shown in the supplementary information (Fig. S 3).

3. Results and discussion 32. UV irradiation

3.1. CN-volatilisation/oxidation Photolysis represents another possible degradation reaction besides


oxidation. Table 2 depicts the results of experiments with three different
The oxidation versus volatilisation of cyanide by atmospheric oxygen irradiation periods.
was followed in two experimental strategies. Similar to the results of the oxidation experiments, the HCN loss in
solution was equal to the amount of absorbed cyanide as a consequence of
volatilisation. The amount of volatilised HCN was in good agreement with
data found in the volatilisation experiments. The half-life calculated from the
data of Table 2 is 95,5 h (SD = 2,2 h). The total amount

Table 1
Half-life (thl) and time constant ofHCN in buffered solutions at different pH (average value ± standard deviation).
pH 14 13 12.6 10.5 9.5 9
12 11 10
t
hl n. d. 440 ± 50 d 176 ± 16 d 53 ± 6d 238 ±17h 107 ± 5h 38.4 ± 1,4 h 11.6 ± 1,2 h 5.0 ± 0,5 h
t
0 n. d. 640 ± 70 d 254 ± 23 d 76 ± 8d 343 ± 24 h 150 ± 6h 55.4 ± 2,3 h 16.7 ± 1,7 h 7.2 ± 0,7 h
1172 A. Bruger et al. / Science of the Total Environment 627 (2018) 1167-1173

Table 2
HCN decrease in a buffered solution (pH: 10.3) and HCN gas absorption after UV irradiation. HCNi: concentration in the buffered soluti on, HCNg concentration in the gas phase identified via
absorption in NaOH. HCNl + HCNg: total amount of HCN after irradiation, c0: initial concentration of cyanide in the buffered solution.

Time HCNl/mg-L-1 HCNg/mg-L-1 Volatilisation/% HCNl + HCNg/mg-L-1 Q)/mg-L 1


24 h 334 65 16.2 399 400
48 h 227 120 30.1 397 398
72 h 237 160 40.3 397 397

of HCN did not change during the experiments using UV light for up to 72 h The cyanide concentrations found in the Quebrada la Cianurada are
irradiation time, no HCN degradation via photolysis was found in these comparable to results from samples of draining waters with similar pH found
experiments. in a gold mine in Sardinia/Italy, that receive seepage from the tailings
impoundment (Da Pelo et al., 2009). The persistence of free cyanide in
stream water has to be considered in the assessment of potential sources
3.3. Ambient air measurements in Segovia
for cyanide contaminations in a wide area. The reduction of the HCN
concentration cannot be reduced to levels below regulatory concern as a
The measurements of the air surrounding gold processing facilities were
result of volatilisation under these conditions (Logsdon et al., 1999).
done at three locations, where cyanide solutions are stored in open tanks
However, for an advanced investigation, sampling at different side streams
and freely accessible. The results as well as the determined concentrations
as well as the screening of the main stream on different locations has to be
of the cyanide solutions in the open tanks with their pH are listed in Table 3.
done. These results will enable us to provide the volatilisation rate of cyanide
Hence with this method it was shown that the TWA limit of 0,9 ppm
for this river.
cyanide is markedly exceeded at all measured areas. A more precise
analysis would be permitted in the extension of the absorption time.
The data collected from the ambient air of small scale goldmines in
4. Conclusions
Segovia as well as the data found for large scale goldmines confirm the
results from laboratory experiments. Further measurements will follow to
The often stated assumption that natural oxidation and photolysis would
determine the extent of the area, where values higher than 1 ppm cyanide
reduce the cyanide content in air to harmless values could not be confirmed
can be found and for the application of our method for the determination of
in areas, where workers have to operate with cyanide solutions. In laboratory
CN concentrations in the air surrounding large scale mines. It is expected
experiments it was shown that the volatilisation is the only process in the
that measurements near leach heaps will yield higher cyanide
cyanide decline of pH buffered solutions in experimental periods up to 13
concentrations due to the higher contact area of cyanide with the
days.
surrounding air and the crushed ores in accordance with measurements
The described method is suitable for the application by local employees
already done in large scale mines. CN concentrations of 5 ppm or higher in
in processing facilities for the determination of the cyanide pollution in the
large scale goldmines should conduct research regarding the cause of the
atmosphere. An air pump together with an absorption flask and a flow meter
HCN-emission sources and lead to the systematic reduction of
could be combined with an existing cyanide-analysis equipment (existent in
contamination sources for the protection of the workers.
many gold processing facilities) to identify areas with possible health risks
for the workers.
3.4. Water analysis in Segovia The results of the cyanide analysis in the creek show that the con-
centrated drains from the surrounding processing facilities are too high to be
Samples from the Quebrada la Cianurada that collects most of the brought to acceptable levels by dilution from the creek or volatilisation.
drains of the town were taken at three different locations. For a comprehensive assessment of the contamination potential of
The cyanide level of the mine stream was considerably higher than the cyanide leaching a mass balance of cyanide is inevitable. The analysis of
values found in the Quebrada la Cianurada. However, this cyanide level did cyanide volatilisation in any process involving this compound in addition to
not change the concentration of the main stream evidently (Table 4). The existing data of the leaching process could lead to these results.
high level of cyanide concentration in the main stream and a comparatively Estimations, without these considerations seem to represent an important
low discharge of the side stream are considered to be the main reasons for factor for a widespread existence of different standards concerning
these results. The existing results indicate high cyanide concentrations in the contamination limits. The localization and collection of data for any relevant
drains of the gold processing facilities. The impact of the cyanide contamination source would be an important contribution to minimize
volatilisation along the stream could not be determined due to the small controversies regarding the hazardousness of the cyanide leaching process
number of measuring points. and to optimize the process operation with a view to minimal contamination.
The high CN-concentration at the location before the contributing mine In small-scale as well as in large-scale gold mining, conflicts as a result of
stream are caused by the processing plants predominantly found inside the different attitudes in gold mining especially related to cyanide leaching can
town. Only a few gold mines have their own processing plants in their mining result in substantial expenses and time delays in the workflow of gold
area. Since the sampling area was downstream outside the town, the processing.
Quebrada la Cianurada is already fed by the discharge from the processing Table 3
Cyanide concentration in the air surrounding three processing tanks and CN concentration in
plants of the town when it passes the area where the samples were taken.
the solutions in the tanks. Containing cyanide leaching solutions.
The results of cyanide analysis in stream water revealed very high
concentrations, compared to common regulations. According to the re- pH in leaching Absorption CN conc. in leaching CN conc. in
solution time/h solution/g-L-1 air/ppm
quirements of the International Cyanide Management Code standards,
Entable JM 12.5 1 0.83 5
cyanide process solution discharges to surface waters should not exceed 12.3 1.04 5
Mina La
0.5 mg/L WAD cyanide nor result in a concentration of free cyanide in 1
Campana
excess of 0.022 mg/L within the receiving surface water body, and Mina 11.6 2 1.32 4
Cogote
downstream of any mixing zone (ICMI, 2009).
A. Bruger et al. / Science of the Total Environment 627 (2018) 1167-1173 1173

Table 4
Cyanide concentration in the Quebrada la Cianurada.

Location before contributing mine stream Mine stream (tributary stream) Location after contributing mine stream
Cyanideconc./mg-L 1 17 30 18
pH 6.5 8.2 7.2

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