Authors' Revised Draft Infacon XV: International Ferro-Alloys Congress, Edited by R.T. Jones, P. den Hoed, & M.W.

Erwee,
Southern African Institute of Mining and Metallurgy, Cape Town, 25–28 February 2018

New insights into Cr(VI) related aspects associated with

FeCr production

P.G. van Zyl1, J.P. Beukes1, S.P. du Preez1, M.M. Loock-Hattingh1 and A.D. Venter1
1Chemical Resource Beneficiation, North-West University, Potchefstroom, South Africa

Abstract – Airborne Cr(VI) is considered a human carcinogen, while the debate regarding
the negative health impacts related to Cr(VI) ingestion is still ongoing. Small amounts of
Cr(VI) are unintentionally formed during several ferrochromium (FeCr) production steps.
In this paper a number of new insights into Cr(VI) related aspects associated with FeCr
production will be presented.
Cr(VI) formation during flaring of closed submerged arch furnace off gas was investigated
for the first time. Results indicated that less Cr(VI) is formed than previously estimated. The
regional impact of airborne Cr(VI) emitted in the western limb of the Bushveld Complex
(wBC) was assessed at a regional background site, which clearly indicated higher levels of
Cr(VI) in air masses that had passed over the wBC than over the regional background. A
Cr(VI) assessment of drinking and surface water pollution in the vicinity of FeCr smelters in
the South African interior proved that most smelters do not impact negatively on drinking
and surface water quality, although exceptions were found. Leachability tests of semi-closed
submerged arc furnace bag filter dust proved that not all Cr(VI) is leached and treated with
the currently applied treatment processes and that an alternative approach needs to be
developed.

Keywords: Airborne Cr(VI), surface and drinking water, flaring, bag filter dust, submerged
arc furnace, air quality

INTRODUCTION
Hexavalent chromium or Cr(VI) is generally considered a human carcinogenic.
However, according to the International Agency for Research on Cancer (IARC) there
seems to be inadequate evidence to support the carcinogenicity of all Cr(VI)
compounds (IARC, 1997). Furthermore, the carcinogenicity of Cr(VI) is mainly
associated with respiratory-induced diseases (Beaver et al., 2009; Thomas et al., 2002),
i.e. airborne Cr(VI), while there seems to be conflict in literature relating to the
carcinogenicity of Cr(VI) in drinking water (Gatto et al., 2010; Stern, 2010).

Cr(VI) can be released into the environment through various anthropogenic (e.g.
Mandiwana et al., 2007) and natural (e.g. Panichev et al., 2008; Oze et al., 2007)
activities, which can manifest in air, soil and water (Bartlett, 1991). Of particular
interest in this paper is Cr(VI) associated with the ferrochromium (FeCr) industries in
South Africa. FeCr is mainly produced by the carbo-thermic reduction of chromite ore,
mostly in submerged arch furnaces (SAFs) or direct current furnaces (DCFs) (Beukes et
al., 2010). South Africa holds a significant portion of the world's viable chromite ore
resources (Kleynhans et al., 2012 and references therein) and is the second largest FeCr-
producing country (Beukes et al., 2012 and references therein). Approximately 80% to
90% of ferrochrome (FeCr) is consumed by the stainless-steel industry, primarily as
high-carbon or charge-grade FeCr (Murthy et al. 2011). Stainless steel is a vital alloy in
various applications (Gasik, 2013), with the Cr content of stainless steel increasing its
corrosion resistance.

1
Although unintentional, small amounts of Cr(VI)-containing species are generated
during the production of FeCr, since oxygen cannot be entirely excluded from all high-
temperature process steps. Beukes et al. (2010) presented a relatively comprehensive
review on the possible generation of Cr(VI) during the various production steps
utilised in FeCr production. Beukes et al. (2010) indicated that small amounts of Cr(VI)
might form during various FeCr production steps, e.g., dry milling of chromite
(Glastonbury et al., 2010; Beukes and Guest, 2001), oxidative sintering of chromite
agglomerates, and during the furnace smelting operation, especially for open or semi-
closed furnaces. This can lead to small amounts of Cr(VI) being present in the off-gas
originating from the smelting process and other high-temperature process steps, and
fumes formed during the tapping process and in the slag. The major wastes associated
with the FeCr industry are slag, as well as bag filter dust (BFD) and venturi sludge
originating from the off-gas (Van Staden et al., 2014). BFD and venturi scrubber sludge
are regarded as hazardous wastes, which are mostly recycled back into the process, or
treated to reduce Cr(VI) and subsequently disposed of in fit-for-purpose waste storage
facilities, e.g., a slimes dam. The Cr(VI) treatment processes applied by the South
African FeCr producers were recently reviewed (Beukes et al., 2012).

The reviews by Beukes et al., (2010), Beukes et al., (2012) and Beukes et al., (2017)
highlighted uncertainties associated with certain production steps and treatments of
wastes that need to be further investigated in order to enhance the current
understanding of Cr(VI) generation during FeCr production. Furthermore, considering
the size of the South African FeCr industry, it is obvious that assessments of possible
local (within the proximity of smelters) and regional Cr(VI) pollution should be
conducted. However, limited studies have been conducted to assess the influence of
FeCr production on the environment. Therefore the aim of this paper is to present a
number of new insights into Cr(VI) related aspects associated with FeCr production.
These aspects include: Cr(VI) generation during the flaring of CO-rich off-gas from
closed submerged arc furnaces (SAF); an assessment of the regional impacts of
atmospheric Cr(VI) pollution; an assessment of Cr(VI) pollution in surface and
drinking water in close proximity to FeCr smelters; and the leaching potential of Cr(VI)
from BFD.

MAJOR SECTION
Cr(VI) generation during flaring of CO-Rich off-Gas from closed FeCr SAF
Off-gas from a closed FeCr SAF is usually cleaned with wet venturi scrubbing, which
removes ~99.9 % of particulate matter (PM) in the off-gas. In certain first-world
countries, the remaining particulate matter is further removed with sintered filters
(Niemela, et al., 2004). However, in most developing countries, this sintered filtering
after wet venture cleaning, has not been implemented. This implies that some Cr-
containing particulate matter will pass through the CO-rich off-gas stack flare, which
could lead to the possible formation of Cr(VI). Currently, almost no data exist in the
peer-reviewed public domain to quantify the conversion of Cr(III) to Cr(VI) during the
flaring process. A conversion of 0.8 to 1% is currently used in environmental impact
assessments (EIA), which is based on a personal communication (Venter and
Liebenberg-Enslin, 2004). In order to partially address the uncertainty relating to Cr(III)
to Cr(VI) conversion during flaring of CO-rich off-gas from closed FeCr SAFs, the
influence of flaring temperature, size of the particles passing through the flare, and
retention time within the flame were investigated in this paper, which were considered
the most important factors within this context. Multiple linear regression was also used

2
to combine the effect of the three parameters investigated to estimate the overall
impact.

Methodology
Two case study chromite ores were used, i.e. a metallurgical grade chromite ore and an
upgraded upper group 2 (UG2), which were obtained from a large FeCr producer in
South Africa. The ores were milled to generate fine particles for which particle size
distribution analyses were performed. The rapid heat exposure associated with FeCr
SAF off-gas flaring was simulated by dropping 5 g of a specific ore type and particle
size fraction sample through a vertically placed tube furnace preset at a specific
temperature (temperature range relevant to closed FeCr SAF off-gas flaring). The top
end of the tube was closed off with a piece of flat ceramic material and only briefly
opened to drop the sample down the tube, where after it was again closed off
immediately to prevent ultra-fine particles being dragged upward due to the chimney
effect. In order to evaluate the effect of retention time on the formation of Cr(VI),
specific samples were dropped multiple times through the furnace tube. Cr (VI) was
extracted from the samples by performing hotplate digestion extraction with a sodium
carbonate and sodium hydroxide buffer solution, while the Cr(VI) content of extracted
samples was determined sing an ion chromatograph (IC) with a post-column 1,5-
diphenylcarbazide (DPC) colorant delivery system (AXP pump) coupled to a uv-visible
absorbance detector. All results were expressed as percentage Cr(VI) conversion, i.e. %
Cr(VI) conversion.

Influence of Temperature, Particle Size and Retention Time on % Cr(VI) Conversion

The effects of temperature on the % Cr(VI) conversion observed for metallurgical grade
and UG2 chromite ore fines are presented in Figures 1 (a) and (b), respectively. The
retention time of the particles in the hot zone of the tube furnace was kept constant at
0.148 seconds, i.e. a single pass. It is evident from Figure 2 that metallurgical grade and
UG2 chromite ore fines exposed to the lowest experimentally investigated temperature
(874.15 K, 600 °C) had the lowest % Cr(VI) conversion with the % Cr(VI) conversions
increasing linearly with an increase in exposure temperature for both ores. The
maximum % Cr(VI) conversion for metallurgical grade and UG2 ores was 3.69x10-3%
and 3.81x10-3%, respectively at 1674.15 K (1400 °C) for the smallest particles (d90 of
45 µm).

(a)

Figure 1: The influence of temperature on % Cr(VI) conversion for all particle size fractions (indicated with
d90 values) of (a) metallurgical grade chromite and (b) UG2 ore fines. The retention time of the particles in
the hot zone of the tube furnace was kept constant at 0.148 seconds, i.e. a single pass.
3
 (b)

Figure 1: Continued

For a constant amount of particulate matter, the surface area will increase as the
particle size decreases, which implies that smaller particles has a larger surface area
that can be oxidized within the off-gas flare. The effects of d90 particle size on % Cr(VI)
conversion for metallurgical grade chromite and UG2 ore fines are presented in Figures
2 (a) and (b), respectively. The metallurgical grade and UG2 ore fines with the largest
d90, (910 µm) had the lowest % Cr(VI) conversion at each of the temperatures
investigated. Thereafter, % Cr(VI) conversion increased almost exponentially with a
decrease in d90 particle size with the highest % Cr(VI) conversion determined for the
d90 of 45 µm size fraction. Fitting of an equation through the afore-mentioned results
indicated that the relationship between % Cr(VI) conversion and particle size had a
power factor dependence with the general format of d90-0.3203.

(a)

Figure 2: The influence of particle size (indicated with d90 values) on % Cr(VI) conversion for all
temperature ranges of (a) metallurgical grade chromite and (b) UG2 ore fines. The retention time of the
particles in the hot zone of the tube furnace was kept constant at 0.148 seconds, i.e. a single pass.

4
 (b)

Figure 2: Continued

To investigate the influence of retention time on % Cr(VI) conversion, the two size
fractions with the largest particles (d90 of 910 µm and 310 µm for metallurgical grade
and d90 of 985 µm and 310 µm for UG2) were exposed to the highest temperature
1674.15 K, 1400 °C) in consecutive multiple drop experiments through the tube furnace.
These larger particles were less prone to the chimney effect, making consecutive
multiple drop experiments feasible. The effects of retention time on % Cr(VI)
conversion for the metallurgical grade chromite and UG2 ore fines are shown in Figure
3, which indicate that increased retention times led to higher % Cr(VI) conversions. At
the longest evaluated retention time (0.594 s), the % Cr conversions ranged from
4.185x10-3% to 6.53x10-3%. Fitting of the afore-mentioned results indicated that the
relationship between % Cr(VI) conversion and retention time had an exponential
dependence with the general format of 0.001075e(2.75754)(Retention time).

Figure 3: The influence of retention time on % Cr(VI) conversion for metallurgical grade chromite and
UG2 ore fines at 1674.15 K (1400°C)

5
Multiple Linear Regression to Calculate Overall % Cr(VI) Conversion

Multiple linear regression (MLR) denotes the relationship between more than one
independent variable (xi) and a dependent variable (y) by the equation:

y = c0 + c1x1 + c2x2 + c3x3+ ....................czxz [1]

where ci represent parameterised constants. In this study, MLR was used to determine
an equation for the dependent variable, i.e. % Cr(VI) conversion (y in Equation 1),
expressed in terms of the investigated independent variables, i.e. flaring temperature,
particle size and retention time (xi in Equation 1). The optimal equation determined
with MLR was

% Cr(VI) conversion = -3.78x10-3 + (1.51x10-6 x T) + (1.07x10-2 x d90-0.3203) + (0.94 x

1.08x10-3e(2.75475)(Retention time)) [2]

where T is the exposure temperature (K), d90 the d90 particle size (µm) of the particulate
matter passing through the tube furnace and Retention time the retention time
(seconds) of particles within the hot zone of the furnace. In Figure 4 (a) and (b) the
experimental and calculated % Cr(VI) conversions for the metallurgical grade chromite
and UG2 ore fines, respectively, are presented. The first six columns indicate % Cr(VI)
conversions as a function of varying particle size (indicated in x-axis) and temperature
(indicated with color) for a fixed retention time (0.148 s), while the last two columns
indicate % Cr(VI) conversions as a function of longer retention times, i.e. from 0.148 to
0.593 s, at a constant temperature (1674.15 K, 1400 ºC). Although there are some
differences between the experimentally determined % Cr(VI) conversions and values
calculated with the MLR Equation 2, it is evident from Figures 4 (a) and 4 (b) that
Equation 2 can be used relatively effectively to determine % Cr(VI) conversions.

(a)

Figure 4: Calculated % Cr(VI) conversion values using Equation 1 compared to experimental values for
(a) metallurgical grade chromite and (b) UG2 ore fines

6
 (b)

Figure 4: Continued

Industrial Relevance and Practical Application

The optimum MLR Equation 2 determined can be used by specific FeCr smelters to
estimate % Cr(VI) conversion more accurately than the present estimations. Since three
independent variables were included in the optimum MLR solution, i.e. retention time,
d90 and temperature, these parameters have to be determined or estimated for such
application. Retention time will depend on the length of the flare and the exit velocity
of the off-gas of which the flare length can be determined using a photo of the stack
flare, with the diameter of the furnace flare stack serving as the scale to calculate the
flare length. The d90 particle size of actual particles can be determined by collecting and
analyzing particles from piping/equipment after the wet venturi scrubber during
maintenance periods. It would not be advisable to collect such particles during
operation, since CO gas is very poisonous and can also result in a CO gas explosion.
The off-gas flare temperature can be determined using an infrared thermometer or
infrared camera to visually determine the temperature, or alternatively it can be
calculated with thermodynamic software based on the actual off-gas composition.

As an example of the practical application, the % Cr(VI) conversion for a typical closed
SAF can be considered. In this example, the retention time of the particulate matter is
1.01 seconds (for 6 m flare and exit velocity of 6 m/s, derived from Figure 1).
According to Niemelä et al. (2004), it is theoretically difficult to remove particles
smaller than 1 µm from the off-gas stream with a wet venturi scrubber; therefore, the
d90 was assumed to be 1 µm. The flaring temperature was assumed to be 2274.15 K
(2000 °C), which is less than the burning temperature of pure CO due to typical
dilution from other gases present in the off-gas, e.g. CO2 and N2. Replacing these
values into Equation 2 yielded a % Cr(VI) conversion of 2.7x10-2 for this specific FeCr
SAF. For an unrealistic worst case scenario, it can be assumed that the retention time is
2.02 seconds (which represents a 12 m flare with an exit velocity of 6 m/s), the d 90
particle size is 0.005 µm (which is an unrealistic small d90 particle size) and the flaring
temperature is the highest temperature obtained from literature/thermodynamic

7
calculations for pure CO combustion, i.e. 2525.35 K (2251.2 °C). Equation 2 yielded a %
Cr(VI) conversion of 3.5x10-1 for this scenario. These calculated values indicate that the
realistic and unrealistic worst case scenario % Cr(VI) conversions are significantly
lower than the % Cr(VI) conversion values currently used in EIAs to determine the
Cr(VI) emissions from FeCr smelters.

Regional atmospheric Cr(VI) pollution from the Bushveld Complex, South Africa
Most of the FeCr smelters in South Africa are concentrated in or close to the Bushveld
Complex (name of the geological structure), which is the largest chromium and
platinum group metals (PGM) deposit in the world (Xiao and Laplante, 2004;
Moskalyk and Alfantazi, 2003). Apart from the FeCr industry, the PGM mining and
metallurgical refining industries in South Africa also consume significant volumes of
chromite ore (Xiao and Laplante, 2004; Cramer et al., 2004). The western limb of the
Bushveld Complex (wBC) is the most exploited, with 11 pyrometallurgical smelters
occurring within an approximate 55 km radius (Venter et al., 2012). Venter et al. (2012)
indicated that air quality in the wBC is problematic, with ozone (O3) and PM 10 (PM
with aerodynamic diameter less than 10 m) regularly exceeding the limits prescribed
by the South African national ambient air quality standards (NAAQS). Relatively
recently, the wBC was also included in a declared air pollution hotspot in terms of the
South African National Environmental Management Act (NEMA): Air Quality, termed
the Waterberg Priority Area
(www.environment.gov.za/sites/default/files/gazetted_notices/nemaqa_waterberg_
declaration_g35435gen495. pdf, accessed 28 February 2016). Notwithstanding the
national and international importance of the wBC, the known air quality issues therein
and the potential for atmospheric Cr(VI) pollution from there, an assessment of
regional atmospheric Cr(VI) pollution from the wBC has not yet been undertaken.

Methodology
Sampling was conducted at the Welgegund atmospheric research station (26°34′10″S,
26°56′21″E, 1480 m AMSL), which is situated approximately 100 km west from
Johannesburg on a commercial farm. Welgegund is situated approximately 105 km
downwind of the nearest pyrometallurgical smelter in the wBC on the dominant anti-
cyclonic recirculation route of air mass over the interior of South Africa (Garstang et
al., 1996), which implies that the site is ideally positioned to determine the regional
effect of air masses that had passed over the wBC (Venter et al., 2017). In addition,
Welgegund is considered to be a regionally representative background site with no
direct impacts from pollution sources in close proximity. Figure 5 depicts the location
of Welgegund within a regional southern African context and the extent of the
Bushveld Complex ore deposits (greyscale areas on the southern African map).

8
 (i) (ii)

Figure 5: (i) The location of Welgegund within a regional southern African context and the extent of the
Bushveld Complex ore deposits (greyscale areas in the southern African map). Additionally, in the
zoomed-in map, the locations of large pyrometallurgical smelters in the wBC, the Johannesburg-Pretoria
megacity (greyscale area in in the zoomed-in map) and large atmospheric point sources in the interior of
South Africa are indicated. (ii) Examples of air masses calculated for a specific 24-hour sample that had
passed over the regional background (a), air masses that had spent at least two hours over the wBC source
region (b) and air masses that had spent at least two hours over the wBC source region, as well as five or
more hours over the large mixed source region (c). The colour bar indicates the frequency of hourly-
arriving back trajectories calculated for a day passing over 0.2° x 0.2° grid cells.

Cr(VI) occurring in atmospheric aerosols was evaluated, since the dispersion of

particulate matter (PM) would be the principal mode of regional Cr(VI) distribution.
Starting at 00:00 am local South African time, daily 24-hour PM2.5 (≤ 2.5 μm) and PM2.5-
10 (2.5-10 μm) samples were automatically collected on PTFE filters with a
Dichotomous Partisol sampler for a full calendar year (1 June 2012 to 31 May 2013).
Collected aerosols samples were extracted from filters with hotplate digestion
extraction with a sodium carbonate and sodium hydroxide buffer solution, while being
purged with nitrogen to prevent inter-conversions between Cr(VI) and Cr(III). Cr(VI)
content of extracted samples was determined sing an ion chromatograph (IC) with a
post-column DPC colorant delivery system coupled to a uv-visible absorbance
detector.

Air mass history was determined by calculating 96-hour back trajectories arriving
hourly at an arrival height of 100 m with the Hybrid Single-Particle Lagrangian
Integrated Trajectory (HYSPLIT) model (version 4.8), developed by the National
Oceanic and Atmospheric Administration (NOAA) Air Resources Laboratory (ARL)
(Draxler and Hess, 2004). In order to link sampled PM with air mass history, two
source regions were defined. The first source region (indicated as the black polygon in
the zoomed-in portion of Figure 5) comprised a relatively small area in the wBC
9
wherein nine pyrometallurgical smelters occurred. The second source region
(indicated as the blue polygon in the zoomed-in portion of Figure 5) encompassed the
Jhb-Pta megacity, as well as the area where most of the very large atmospheric point
sources (e.g. coal-fired power stations, petrochemical operations and other
pyrometallurgical smelters) occur in the South African interior. Individually calculated
hourly-arriving back trajectories for each 24-hour sample period were then overlaid on
a map that was divided into 0.2° x 0.2° grid cells. On these maps, a colour code
indicated the number of trajectories passing over each 0.2° x 0.2° grid cell, with red
being the highest number. These 24-hour sampling period overlay back trajectory
maps were then visualised and sorted into three categories, i.e. 1) air masses that only
passed over the regional background mainly between north and south, to the west of
Welgegund (Figure 5 (ii) a); 2) air masses that had spent at least two hours over the
source region defined in the wBC ((Figure 5 (ii) b); and 3) air masses that had spent at
least two hours over the source region defined in the wBC, as well as five or more
hours over the large mixed source region defined in Figure 5 ((Figure 5 (ii) c). Samples
for which air masses that did not represent the regional background (category 1), but
also did not qualify for category 2 or 3 were not considered further.

Results and discussion

Atmospheric Cr(VI) concentrations in the PM2.5 and PM2.5-10 samples associated with air
masses that were classified as passing over the regional background (category 3, Figure
5, 53 samples) were below the detection limit (0.84 ng/m3) of the analytical instrument.
In contrast, Cr(VI) in samples associated with air masses passing over the wBC source
region (category 2, Figure 5, 21 samples) or the mixed region (category 3, Figure 5, 23
samples) was substantially higher. The PM10 (PM2.5 + PM2.5-10) of air masses that had
passed over both the wBC source region (category 2, Figure 5) and those that had
passed over the mixed region (category 3, Figure 5) had median Cr(VI) concentrations
of 4.6 ng/m3. This is higher than the average of 0.044 ng/m3 for Washington DC (Tirez
et al., 2011 and references therein) and the range reported for Vienna, i.e. 0.04 to 0.23
ng/m3 (Hagendorfer and Uhl, 2007). However, the concentrations were in the same
order as atmospheric Cr(VI) reported for a site in Northern Italy and at an industrial
site in Tunis that had concentrations ranging between 0.68 and 3.68, and 5.4 and 7.8
ng/m3 (Catrambone et al., 2013), respectively, as well as at two sites near a stainless
steel production facility in Belgium that reported 90th percentiles of 3.5 and 14 ng/m3
(Tirez et al., 2011).

Figure 6 presents the statistical distribution of Cr(VI) in both the PM2.5 and PM2.5-10 size
fractions, as well as the combined PM10 fractions. It is evident that the majority of the
Cr(VI) is present in the PM2.5 fraction, with Cr(VI) in the PM2.5-10 size fraction in certain
instances below the detection limit. This concentration distribution is attributed to two
reasons. 1) Most of the pyrometallurgical processes potentially releasing PM-
containing Cr(VI) will emit very fine PM. The Cr(VI)-containing particles in the off-gas
from open and semi-closed SAFs, or from closed SAFs and DCFs, are removed with
bag filters and wet venturi scrubbers, respectively (Beukes et al., 2012; Niemelä et al.,
2004). These systems remove 99.9 % of PM from the off-gas, but are not very effective
in capturing PM1 (Niemelä et al., 2004). Additionally, Cr(III) in the PM1 that passes
through the flare of the CO-rich off-gas originating from closed SAFs or DCFs being
burned may be oxidised resulting in the formation of Cr(VI) (Du Preez et al., 2015). 2)
Finer particles have longer atmospheric lifetimes than coarser particles. Therefore,
even if coarser Cr(VI)-containing particles are released by mining and metallurgical
activities in the wBC, these particles will be removed from the atmosphere relatively
quickly, preventing their transport to the Welgegund research station.

10
Figure 6: Cr(VI) concentrations in PM2.5 (≤ 2.5 μm), PM2.5-10 (2.5-10 μm) and PM10 (sum of PM2.5 and PM2.5-
10) associated with air masses that had passed over the wBC- and mixed source regions. The red line
indicates the median, the black dot the mean, the blue rectangle the 25 th and 75th percentiles, the whiskers
± 2.7 times the standard deviation and the horizontal black dashed line the detection limit

The spread of Cr(VI) concentrations in air masses that had passed over the wBC source
region (category 1, Figure 5) were also much smaller than that of the mixed region.
This smaller spread for the wBC source region is indicative of the similar types of
sources within this area. Air masses that had passed over the mixed source region
(category 3, Figure 5) occasionally had higher Cr(VI) concentrations than that of the
wBC source region, indicating the existence of other potential sources of Cr(VI) in the
mixed region. It is well known that relatively low grade coal with reasonably high ash
content (Jeffrey, 2005) is consumed in South Africa for both industrial activities and for
household space heating in semi- and informal settlements (Hersey et al., 2015; Venter
et al., 2012). These sources could potentially also emit atmospheric Cr(VI) in the mixed
source region.

Cr(VI) contamination of surface water in the proximity of FeCr smelters

Due to the aqueous solubility of most Cr(VI) compounds (Ashley et al., 2003), soil and
air contamination can eventually result in water contamination, due to Cr(VI) leaching
from soils, as well as dry and wet deposition of atmospheric particles containing
Cr(VI). Drinking water standards for total chromium and Cr(VI) have been adopted by
various countries and range between 3 μg/L and 100 μg/L (Ma and Garbers-Craig,
2006). The South African drinking water standards for total chromium and Cr(VI) are
100 and 50 μg/L, respectively. In an effort to determine the extent of Cr(VI) pollution
in the proximity of FeCr smelters in South Africa, surface water close to FeCr smelters
was evaluated over a period of 1 year. Although it was not the primary focus, drinking
water was also considered to at least indicate problematic areas. The intention was not
to implicate any specific FeCr smelter or company, but rather to get a general picture of
the extent of possible Cr(VI) pollution. It is hoped that data presented could be used to
rectify possible problematic areas and thereby promote the sustainable development of
the FeCr industry in South Africa.

Methodology
Surface- and drinking water were samples were collected at 10 and 11 FeCr smelters,
respectively, of the 14 FeCr smelters in South Africa indicated in Figure 7(i). In order to
limit seasonal bias, sampling was conducted monthly for a full year, i.e. February 2011

11
to January 2012. Certain limitations had to be considered during sampling site selection
for surface water to make the study logistically feasible and scientifically creditable,
which included: (a) sampling had to be logistically possible to enable monthly
sampling campaigns; (b) the study was conducted without prior notice to the FeCr
industry and private landowners in the vicinity of the FeCr smelters to ensure that the
FeCr industry did not alter their operation in any manner to bias the results; (c) the
sites were selected to ensure easy access without trespassing on private property; (d)
consideration had to be given to the safety aspects during monthly sampling; (e) as far
as possible, the directional flow of surface water drainage patterns was considered; (f)
the sampling sites were selected to also capture possible spillages from the appropriate
waste collection facilities and surface run-off from the smelters, where possible.

Sampling site selection for the drinking water sites was much less complicated, since
samples were collected from restroom facilities accessible to the general public at filling
stations as close as possible to the relevant smelters. It is assumed that drinking water
obtained from such facilities would be representative of drinking water consumed by
the population in the area close to that specific sampling site. In Figure 7 (ii) a to c
maps indicating the surface- and drinking water sites in proximity to the FeCr smelters
are presented, which are also indicated in rectangular blocks in Figure 7 (i). The FeCr
smelters were numbered 1 to 12 with surface- and drinking water sampling sites
numbered accordingly. At the FeCr smelters numbered 4, 5, 7 and 9, two surface water
sampling sites were located, which were distinguished by indicating them as sampling
sites “a” and “b”. The authors refrained from referring to company, town/city and
river names that could be used to implicate any specific smelter.

(i)

Figure 7: (i) A South African map indicating the location of FeCr smelters with black dots. The proximity
of most of these smelters to the Bushveld Complex, which is indicated in grey, is also illustrated.
Additionally, three areas have been indicated with rectangular blocks. (ii) Location of the surface- (green
squares) and drinking water sampling sites (red diamonds) in relation to FeCr smelters (black dots) and
rivers/streams (blue lines). These enlarged map areas correlated with the three rectangular blocks
indicated in the regional map (Fig. 1)

12
 (ii)

Figure 7: Continued

At each sampling site, three samples were collected each month for Cr(VI) analysis.
The sample collection and preservation procedures involved pH adjustment if required
(US Environmental Protection Agency (EPA) method 218.6, 1994) as well as
transportation/storage below 4 °C, to prevent Cr(VI)-Cr(III) inter-conversions. One of
the afore-mentioned three samples was also spiked with a predetermined amount of
Cr(VI) to confirm that not Cr(VI)-Cr(III) inter-conversions occurred. Cr(VI) analyses
were conducted with an ion chromatograph (IC) with a post-column
diphenylcarbazide colorant delivery system (AXP pump) coupled to an ultraviolet-
visible (uv-vis) absorbance detector.

Surface water
In Figure 8(a) the surface water Cr(VI) results are presented. In order to facilitate the
discussions of the surface water results, sites with similar Cr(VI) concentration levels
and/or temporal variability of these concentration levels were grouped together into
six groups, i.e. site(s) that had:
• no Cr(VI) concentrations above the detection limit of the analytical
technique;
• Cr(VI) concentrations below the detection limit for most of the time;
• significant Cr(VI) concentrations that never exceeded the South African
drinking water limit, which were also relatively variable over time;
• significant Cr(VI) concentrations that did not exceed the South African
drinking water limit, but which were consistent in terms of temporal
variability;
• significant Cr(VI) concentrations that exceeded the South African
drinking water limit on one occasion, which were also relatively variable
over time;
• significant C(VI) concentrations that exceeded the South African drinking
water limit on several occasions, which exhibited relatively consistent
temporal variation.
13
The temporal variation of Cr(VI) concentrations in surface water of the sites grouped
together is presented in Figure 8 (b).

(a)

(b)

14
 (c)

Figure 8 : (a) Statistical representation of the Cr(VI) concentrations obtained at each of the surface water
sampling sites. (b) Temporal variation of the Cr(VI) concentrations in the surface water at sampling sites
for February 2011 to January 2012. (c) Statistical representation of the Cr(VI) concentrations obtained at
each of the drinking water sampling sites. In (a) and (c) the median Cr(VI) concentration is indicated by
the short horizontal line, the mean by the dot, the maximum the cross, the top and bottom edges of the box
the annual 25th and 75th percentiles, while the whiskers indicate ±2.7σ (or 99.3% coverage if the data has a
normal distribution. The number of samples considered for each sampling sites are also indicated at the
top edge of the graph. The continuous horizontal line indicates the current South African Cr(VI) drinking
water limit, i.e. 50 µg/L

It is evident from the surface water results presented in Figure 8 (a) that sampling sites
4a, 5a, 6, 7a and 10 always had Cr(VI) concentrations below the detection limit of the
analytical technique employed. Surface water sampling sites 1, 8, 9a, 9b and 11 also had
annual mean and median concentrations below the detection limit of the analytical
technique employed. However, for these sites, there were certain months during
which the Cr(VI) levels were above the detection limit (Figure 8b). This indicates that
the surface water at these sites might occasionally be influenced by a Cr(VI) source(s),
although the maximum Cr(VI) levels measured were well below the South African
drinking water limit. Surface water sampling site 3 had relatively low Cr(VI) levels
above the detection limit. However, there were several months during which the
Cr(VI) concentrations were higher with the highest Cr(VI) concentration of 40.9 µg/L
recorded during February 2011.

Surface water sampling site 5b was consistently impacted by Cr(VI) pollution, with
annual mean and median Cr(VI) concentrations being 6.2 and 6.3 µg/L, respectively.
These relatively low mean and median values indicate that Cr(VI) pollution at this site
is limited at present. However, if the consistent presence of Cr(VI) at surface water
sampling site 5b (a river close to FeCr plant 5) is compared to the lack of any Cr(VI) at
surface water sampling site 5a (a cement lined irrigation waterway close to FeCr plant
5), it becomes apparent that these two sites are influenced in different ways although
the sampling sites are just 1.25 km apart. Since site 5a is a lined cement waterway,
groundwater leaching is unlikely to contribute to pollution of the surface water.
However, surface water sampling site 5b can be impacted by groundwater leaching,
since the river system is unlined.

Surface water sampling site 7b was not consistently impacted by Cr(VI) pollution
(Figure 8a). Cr(VI) levels were below the detection limit for five months. For six
months Cr(VI) concentrations were above the detection limit, but were relatively low.

15
However, during July 2011, the Cr(VI) concentrations escalated to a maximum value of
219.6 µg/ℓ, which should be considered as serious. These erratic Cr(VI) concentrations
measured at site 7b indicate that there is a significant anthropogenic Cr(VI) source that
influences the site on occasion. The anthropogenic nature of the Cr(VI) source is also
supported by the observation that the Cr(VI) concentrations at surface sampling site 7a,
which was upstream of FeCr smelter 7, were always below the detection limit.

Cr(VI) concentrations of surface water sampling site 4b were also erratic, as indicated
by a large statistical spread in the results (Figure 8a) and the temporal behaviour
(Figure 8b) also indicated large variations. During February, March, April 2011 and
January 2012, the Cr(VI) levels were below the detection limit. Cr(VI) concentrations
were above the detection limit and relatively low during May, July, October and
December 2011. However, during June, August and September 2011, the Cr(VI)
concentrations increased to monthly average values of 188.6, 193.4 and 69.5 µg/ℓ,
respectively. Similar to surface water sampling site 7b, these erratic Cr(VI)
concentrations at surface water sampling site 4b indicate that there is a significant
anthropogenic Cr(VI) source that influences the site occasionally. This is also
supported by the observation that the Cr(VI) concentrations at surface sampling site 4a
(upstream of FeCr plant 4) were always below the detection limit.

Drinking water
In Figure 8 (c), the drinking water Cr(VI) results obtained are presented. It is evident
that no significant Cr(VI) concentrations were detected at any of the drinking water
sampling sites except at sites 4, 11 and 12. Drinking water sampling site 4 was
consistently impacted by Cr(VI) pollution, which is clearly indicated by the relatively
small statistical spread in Figure 8 (c). It is recommended that, as a precautionary step,
the source of this Cr(VI) drinking water pollution should be investigated and
addressed as an important future perspective, which was not assessed in this study.
The drinking water sampling sites 11 and 12 are significantly impacted by Cr(VI)
pollution. This was particularly significant at drinking water site 11, which has annual
mean and median values of 43.1 and 45.3 µg/L, respectively. The maximum
concentration obtained during November 2011, i.e. 68.1 µg/L, was well above the
drinking water limit. This site was also in close proximity of a primary school less than
1.1 km from site 11 and the origin of Cr(VI) pollution was therefore further
investigated.

Cr(VI) pollution in the drinking water at site 11 did not seem to be related to the major
surface water source, i.e. a perennial river in the area, since the annual mean and
median Cr(VI) concentrations in this river at surface sampling sites 10 and 11 were
below the detection limit. However, further onsite investigation revealed that the
drinking water at sampling site 11 was obtained from a borehole. This additional
information indicated that groundwater in the proximity of smelter 11 was polluted
with Cr(VI), while the major surface water source was not significantly affected. The
management of FeCr smelter 11 was approached who indicated that they and the
appropriate authorities were aware of the afore-mentioned groundwater pollution and
that it occurred due to historic miss-management of waste, which has since been
addressed. However, the additional data supplied through this study indicated that
groundwater at drinking water sampling site 11 was also impacted, although their
assessment model did not indicate it. Therefore, the groundwater abstraction scheme
and supply of clean drinking to affected communities were further expanded to
include the affected area.

16
Aqueous solubility of Cr(VI) compounds in FeCr BFD
In contrast to slag and sludge wastes generated during FeCr production, BFD
generated during the cleaning of off-gas from open/semi-closed FeCr furnaces
contains significant levels of Cr(VI) (Beukes et al., 2012), which cannot be disposed
without proper Cr(VI) treatment (Beukes et al., 2012). After the BFD is treated to
reduce Cr(VI), it is usually disposed in fit-for-purpose waste facilities such as slimes
dams. Treatment of BFD (and indeed any Cr(VI) containing FeCr waste) usually
involve the aqueous reduction of Cr(VI) with an appropriate inorganic reducing agent
such as Fe(II) (Buerge and Hug, 1997) and S(IV) (Beukes et al., 2000 and 1999), or
bacterial reduction (Dhal et al., 2013). Although Cr(VI) can also be reduced with
numerous organic compounds (Kassem, 2010; March, 1992), this is usually avoided
due to the potential solubilisation of Cr(III) (Beukes et al., 2012). The leaching potential
of Cr(VI) from BFD was investigated, which was proven to be a major limitation in the
effectiveness of the conventional Cr(VI) treatment used by industry.

Methodology
Four different BFD samples were obtained from FeCr producers in South Africa, which
were characterised with particle size distribution, scanning electron microscopy (SEM),
X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) analysis. Cr(IV)
species were extracted from BFD samples in a deionised water leaching solution that
has been adjusted to a predetermined pH value. The leaching solutions were purged
with N2 prior to Cr(VI) extraction and then agitated with a magnetic stirrer for 2 hr
during which N2 was continually purged through the system. After Cr(VI) extraction,
the leaching solution were filtered, transferred to volumetric flasks and diluted with
pH adjusted deionized water. In addition to Cr(VI) extraction at specific pH values,
Cr(VI) extractions were also performed using hot plate digestion. A buffer of 0.05M
(NH4)2SO4 and 0.05M NH4OH was used to leached water soluble and sparingly water
soluble Cr(VI) compounds, while a buffer of 3 wt % Na2CO3 and 2 wt % NaOH was
used to leach total Cr(VI) (Ashley et al., 2003; NIOSH 7605, 2003). Half of each
extracted solution was analysed for total aqueous trace metal concentrations
(irrespective of oxidation state), which was performed with inductively coupled
plasma mass spectroscopy (ICP-MS). The other half was used for Cr(VI) analysis,
which was conducted with an ion IC with a post-column DPC colorant delivery system
coupled to a uv-visible absorbance detector.

Trace metal and Cr(VI) leachability

It is generally accepted that higher concentrations of most heavy and transitional
metals will leach out of a solid matrix (e.g. waste and soil) at low pH values (Ding et
al., 2014; Lee et al., 2012). This was also observed experimentally as indicated in
Figures 9 and 10, which present the log concentrations for the alkali/alkali earth and
transition/heavy metals, respectively as a function of pH (Na contents were excluded
at pH > 7, since NaOH solution was used to increase the pH of the leach solutions).
When comparing metal concentrations presented in Figure 9 to concentrations
presented in Figure 10, it is evident that most alkali and alkali earth metals, excluding
Ba, were present in much higher concentrations than transition and heavy metals,
except for Zn that had concentrations comparable to alkali and alkali earth metals,
especially at very low pH.

17
 (a)

(b)

Figure 9 : Log concentration of alkali and alkali earth metals in (a) BFDs A and B, as well as (b) BFDs C
and D, as a function of leach solution pH

18
 (a)

(b)

Figure 10 : Log concentration of transition and heavy metals present in (a) BFD A and B, as well as (b) C
and D as a function of leach solution pH

Cr(VI) leachability
Figure 11(a) presents the leachable Cr(VI) concentrations as a function of leach solution
pH, as well as the two solubility fractions, i.e., combined water soluble and sparingly
water soluble Cr(VI), as well as total Cr(VI) determined. Figure 11(b) indicates the
same data normalized to percentage, based on the total extractable Cr(VI) of each
sample. From these results, it is evident that the amount and percentage of leachable
Cr(VI) increased with an increase in leach solution pH at pH ≥ 9. This is in contrast to
the results obtained for all the other metals for which the leachability increased as the
leach solution pH decreased.

19
 (a)

(b)

Figure 11 : (a) Leachable Cr(VI) as a function of leach solution pH, combined water soluble and sparingly
water soluble Cr(VI), as well as total Cr(VI). (b) The same data normalized to % Cr(VI), based on the total
extractable Cr(VI)

From the data presented in Figure 9, 10 and 11 it is impossible to shed any light on the
possible association of anionic CrO42– with cations, to indicate the identity of the Cr(VI)
compounds that are present in the BFD samples. However, the observed increase of
leachable Cr(VI) with an increase in pH is an indication that not only water soluble
(e.g. Na2CrO4, K2CrO4), but also sparingly water soluble (e.g. CaCrO4, SrCrO4) and
water insoluble (e.g. BaCrO4, PbCrO4) Cr(VI) compounds occur in the samples

20
evaluated. This data can also be used to estimate the average water soluble, sparingly
water insoluble and water insoluble fractions. As is evident from Figure 13(b), there
was no statistically significant difference in the extractable Cr(VI) at pH ≤9, with
approximately 31% of the total Cr(VI) being extracted in this range. This represents the
water soluble Cr(VI) fraction. On average, approximately 65% of the total Cr(VI) was
present as a combination of water soluble and sparingly water soluble compounds.
The difference between these two factions, i.e. 34%, therefore represent the percentage
of sparingly water soluble Cr(VI) compounds. The difference between the total Cr(VI)
(100%) and the combined water soluble and sparingly water soluble fractions (65%)
revealed the presence of approximately 35% water insoluble Cr(VI) compounds in the
BFD samples evaluated.

These above-mentioned results, and in particular the presence of substantial fractions

of sparingly and water insoluble Cr(VI) compounds, contradict the general perception
that total Cr(VI) extraction from ferrochrome BFD can be achieved by neutral or acidic
aqueous extractions. For instance, Maine et al. (2005) indicated that >100 hrs of
extraction is required with neutral water to completely extract Cr(VI) from BFD, while
Gericke (1995) maintained that 24 hr leaching with aqueous solutions of pH 2 to 6 is
adequate for Cr(VI) extraction from BFD. However, none of these authors used buffers
and extraction methods to ensure extraction of sparingly and water insoluble Cr(VI)
compounds (Ashley et al., 2003).

Apart from the above-mentioned possible underestimation of the amount of Cr(VI)

present in BFD by previous studies, the retention times applied in some studies (Maine
et al., 2005; Gericke, 1995) are unpractical. Some FeCr producers pump their BFD
sludge (BFD after being contacted with water) directly to a thickener to separate the
solid particles from the process water, while others might have a small surge tank to
regulate the pumping of the afore-mentioned BFD sludge to the thickener. Typically,
chemical Cr(VI) treatment takes place just prior to the BFD sludge entering the
thickener. Currently, ferrous sulphate of Cr(VI) is the most commonly applied
treatment method (Beukes et al., 2012). However, Fe(II) that is not consumed to reduce
Cr(VI) is oxidized within a couple of minutes to Fe(III), at the pH levels applicable to
FeCr process water (Beukes et al., 2012; Buerge and Hug., 1997). Therefore, the
effective residence time of the BFD particles in the process water, during which Cr(VI)
extraction can take place, is far less than the 2 hrs extraction time applied in this study.
Considering the afore-mentioned description, it is evident that it is highly likely that
the short extraction times associated with current Cr(VI) treatment strategies of FeCr
producers only allow the extraction of the water soluble Cr(VI) fraction.

According to a survey conducted by Beukes et al. (2012) at various FeCr producers, the
pH of FeCr process waters usually vary between 6.2 and 9.0. As indicated in Figure
11(b), as well the discussions thereafter, approximately 31% of the total Cr(VI) is
leached at pH ≤9, which correlates with the water soluble Cr(VI) fraction. Therefore the
currently applied Cr(VI) treatment strategies extract only the water soluble Cr(VI)
fraction, even if extended extraction times are applied.

CONCLUSIONS
Three parameters considered to be critical during flaring, i.e. retention time of the
particles in the hot zone, size of particulate matter passing through the hot zone (d90)
and temperature of the hot zone were experimentally investigated in a tube furnace.
MLR analysis indicated that retention time had the greatest impact on % Cr(VI)

21
conversion, followed by particle size and temperature. From the MLR analysis, an
optimal equation containing all three the investigated independent variables was
determined, which was subsequently used to calculated % Cr(VI) conversions that
compared well to the experimentally determined values. Thereafter, this equation was
used to determine % Cr(VI) conversions for closed FeCr SAFs, which yielded 2.7x10-2
and 3.5x10-1 for realistic and unrealistic worst case scenarios, respectively. The overall
% Cr(VI) conversions obtained from Equation 1 represent a much more reliable
representation than the unsubstantiated % Cr(VI) conversion currently being used in
EIAs for FeCr smelters, i.e. 0.8 to 1%. In future, the Cr(VI) conversion of a specific FeCr
smelter can be calculated utilizing Equation 1. This conversion factor can then be
included as an emission factor in an atmospheric dispersion model applied during an
EIA to determine the Cr(VI) levels to which communities will be exposed.

Ambient atmospheric Cr(VI) concentrations measured at a regional background site for

the first time in South Africa indicated that ambient Cr(VI) concentrations in air masses
that had passed over the regional background were below the detection limit. In
contrast, air masses that had passed over the wBC and/or the mixed source regions
had elevated Cr(VI) concentrations with an average of 4.6 ng/m3. The majority of
Cr(VI) was found to be in the finer size fraction, which could be explained by the
nature of Cr(VI)-containing PM being emitted by the sources in the wBC source region
and the atmospheric lifetimes of different PM size fractions. The results further
indicated that not only pyrometallurgical sources in the wBC, but also other
combustion sources outside the wBC could have contributed to the measured
atmospheric Cr(VI). It is recommended in future studies that simultaneous
measurements of atmospheric Cr(VI) concentrations in both the wBC and also at
Welgegund could be carried out in future to quantify the range of atmospheric Cr(VI)
half-life more precisely. In addition, since numerous meteorological parameters are
measured at Welgegund, multivariate data analysis methods could be applied to such
a dataset to determine the effect of, for instance, relative humidity and temperature on
the atmospheric half-life of Cr(VI).

A relatively comprehensive survey of Cr(VI) pollution in surface water indicated that

surface water in the proximity of most FeCr smelters was unaffected by Cr(VI)
pollution. Two sampling sites indicated consistent impacts by Cr(VI) pollution, but
annual mean values were relatively low (4.4 and 6.3 µg/L) with no values exceeding
the 50 µg/L drinking water limit. However, for two surface water sampling sites
maximum monthly Cr(VI) concentrations of 198 and 220 µg/L were measured. Cr(VI)
pollution of the surface water at these sites were erratic and most likely due to surface
run-off due to poor wastewater management. Such pollution events of the surface
water in the proximity of these FeCr smelters have to be prevented. Results also
indicated that drinking water in the proximity of most FeCr smelters was not polluted
by Cr(VI). However, the annual mean Cr(VI) concentration of drinking water at one
sampling site was 45.3 µg/L, with several months exceeding the 50 µg/L limit. Further
investigation proved that the drinking water at this site originated from a borehole,
which was impacted by a Cr(VI) groundwater plume. Significant steps have, however,
already been taken to remedy the situation in the proximity of this smelter. In order to
better quantify the extent of Cr(VI) pollution around affected sites, groundwater
studies would be required and should therefore be considered as an important future
perspective.

Finally it was indicated that the currently applied Cr(VI) treatment strategies of FeCr
production (with process water pH ≤9) only effectively extract and treat the water
soluble Cr(VI) compounds from the BFD, which represent approximately 31% of the
22
total Cr(VI) present in the BFD samples evaluated. It is therefore critical that improved
Cr(VI) treatment strategies are formulated that would extract all of the Cr(VI) from
BFDs. The results presented suggest that extraction at pH 13 would be required to
solubilise the sparingly water soluble Cr(VI) species from BFD, which will ensure that
sparingly water soluble Cr(VI) compound do not leach from the waste storage facilities
(e.g. slimes dams). Otherwise, there is the potential of Cr(VI) releases over time, which
has been proven to results in environmental Cr(VI) pollution (Loock-Hatting et al.,
2015; Loock et al., 2014). However, it is highly unlikely that such high process water
pH would be economically feasible. Additionally, it is well known from literature that
Fe(II), currently the most commonly employed chemical reductant of Cr(VI), oxidizes
very quickly with dissolved oxygen at such high pH levels. Therefore, the
effectiveness of this and other potential reductants at elevated pH levels needs to be
investigated. Furthermore, the need to extract the water insoluble Cr(VI) species prior
to chemical reduction should be investigated in greater detail, in order to assess the
likelihood of such species being mobilised over extended time periods relevant to
waste disposal facilities.

ACKNOWLEDGEMENTS
This conference paper is based on a synopsis of four papers (Du Preez, et al., 2015;
Venter et al., 2016; Loock et al., 2014; Du Preez et al., 2017) recently published in peer
reviewed internationally accredited journals. Reference to this conference paper should
therefore also include reference to the afore-mentioned papers. Use of content from
Springer (Du Preez et al. 2015), Elsevier (Venter et al., 2016) and Water SA (Loock et al.,
2014; Du Preez et al., 2017) is acknowledged. Financial assistance by the South African
National Research Foundation (NRF) towards the studies of S.P. du Preez and A.D.
Venter is acknowledged. Opinions expressed and conclusions arrived at are those of
the authors and are not necessarily to be attributed to the NRF. The authors also
acknowledge financial support by the Academy of Finland Centre of Excellence (grant
no. 272041) for Welgegund. The authors of this paper also wish to thank the four FeCr
production facilities that provided the BFD case study samples that were used.

REFERENCES
Ashley, K. Howe, A.M., Demangec, M., Nygren O., 2003. Sampling and analysis considerations for the
determination of hexavalent chromium in workplace air. J. Environ. Monit. 5, 707–716,
doi:10.1039/b306105c.
Beaver, L.M., Stemmy, E.J., Constant, S.L., Schwartz, A., Little, L.G., Gigley, J.P., Chun, G., Sugden, K.D.,
Ceryak, S.M., Patierno, S.R., 2009. Lung injury, inflammation and Akt signaling following inhalation
of particulate hexavalent chromium. Toxicol. Appl. Pharmacol. 235, 47–56,
doi:10.1016/j.taap.2008.11.018.
Beukes, J.P., Pienaar, J.J., Lachmann, G., Giesekke, G.W. 1999. The reduction of hexavalent chromium by
sulphite in wastewater. Water SA 25(3) 363-370.
Beukes, J.P., Pienaar, J.J., Lachmann, G. 2000. The reduction of hexavalent chromium by sulphite in
wastewater – An explanation of the observed reactivity pattern. Water SA 26(3) 393-396.
Beukes, J.P., Dawson, N.F., Van Zyl, P.G., 2010. Theoretical and practical aspects of Cr(VI) in the South
African ferrochrome industry. J. S. Afr. Inst. Min. Metall. 110, 743-750.
Beukes, J.P., Du Preez, S.P., Van Zyl, P.G., Paktunc, D., Fabritius, T., Päätalo, M., Cramer, M., Review of
Cr(VI) environmental practices in the chromite mining and smelting industry – Relevance to
development of the Ring of Fire, Canada. Journal of Cleaner Production, 165: 874–889, 2017,
doi:10.1016/j.jclepro.2017.07.176
Beukes, J.P., Van Zyl, P.G., Ras, M., 2012. Treatment of Cr(VI)-containing wastes in the South African
ferrochrome industry – a review of currently applied methods. J. S. Afr. Inst. Min. Metall. 112, 413-
418.
Buerge, I.J., Hug, S.J. 1997. Kinetics and pH dependence of chromium(VI) reduction by iron(II).
Environmental Science and Technology 31 1426-1432.

23
Catrambone, M., Canepari S., Perrino C., 2013. Determination of Cr(III), Cr(VI) and total chromium in
atmospheric aerosol samples. E3S Web of Conferences 1, doi: 10.1051/e3sconf/20130107005
Cramer, L.A., Basson, J., Nelson L.R. 2004. The impact of platinum production from UG2 ore on
ferrochrome production in South Africa. J. S. Afr. Inst. Min. Metall. October 2004, 517-527.
Dhal, B., Das, N.N., Thatoi, H.N. and Pandey, B.D. 2013. Characterizing toxic Cr(VI) contamination in
chromite mine overburden dump and its bacterial remediation. J. Hazard. Mater. 260 141–149.
DOI:10.1016/j.jhazmat.2013.04.050.
Ding, Y., Song, Z., Feng, R. and Guo, J. 2014. Interaction of organic acids and pH on multi-heavy metal
extraction from alkaline and acid mine soils. Int. J. Environ. Sci. Te. 11 33–42. DOI:10.1007/s13762-013-
0433-7.
Draxler, R. R., Hess, G. D., 2004. Description of the HYSPLIT 4 modelling system, NOAA Technical
Memorandum ERL ARL–224.
Du Preez, S.P., Beukes, J.P., Van Zyl, P.G., 2015. Cr(VI) generation during flaring of CO-rich off-gas from
closed ferrochromium submerged arc furnaces. Metall. Mater. Trans. 46B, 1002-1010, doi:
10.1007/s11663-014-0244-3.
Garstang, M., Tyson, M., Swap, R., Edwards, M., Kållberg, P., Lindesay, J.A., 1996. Horizontal and vertical
transport of air over southern Africa, J. Geophys. Res., 101, 23721-23736.
Gasik, M. 2013. Handbook of ferroalloys: theory and technology, Butterworth-Heinemann.
Gatto NM, Kelsh MA, Mai DH, Suh M, Proctor DM (2010) Occupational exposure to hexavalent
chromium and cancers of the gastrointestinal tract: A meta-analysis. Cancer Epidemiology 34 388-
399.
Gericke, W.A. 1995. Environmental aspects of ferrochrome production. In: Proceedings of the 7th International
Ferroalloys Congress, Trondheim, Norway, p. 131–140.
Glastonbury, R.I., Van der Merwe, W., Beukes, J.P., Van Zyl, P.G., Lachmann, G., Steenkamp, C.J.H.,
Dawson, N.F., Stewart, H.M. 2010 Cr(VI) generation during sample preparation of solid samples – A
chromite ore case study. Water SA 36 105-109.
Hagendorfer, H., Uhl, M., 2007. Speciation of chromium in particulate matter (PM 10): development of a
routine procedure, impact of transport and toxicological relevance. Umweltbundesamt, Vienna, REP-
0111, p. 29.
Hersey, S.P., Garland, R.M., Crosbie, E., Shingler, T., Sorooshian, A., Piketh, S., Burger, R., 2015. An
overview of regional and local characteristics of aerosols in South Africa using satellite, ground, and
modeling data. Atmos. Chem. Phys. 15, 4259-4278, doi: 10.5194/acp-15-4259-2015.
IARC (International Agency for Research on Cancer) (1997) World Health Organization. IARC
monographs on the evaluation of carcinogenic risks to humans, Chromium, Nickel and Welding 49.
36 pp.
Jeffrey, L.S., 2005. Characterization of the coal resources of South Africa. J. S. Afr. Inst. Min. Metall., 95-102.
Kassem, T.S. 2010. Kinetics and thermodynamic treatments of the reduction of hexavalent to trivalent
chromium in presence of organic sulphide compounds. Desalination. 258 206–218.
DOI:10.1016/j.desal.2010.03.011.
Kleynhans, E.L.J., Beukes, J.P., Van Zyl, P.G., Kestens, P.H.I., Langa, J.M., 2012. Unique challenges of clay
binders in a pelletised chromite pre-reduction process, Miner. Eng., 34, 55-62, doi:
10.1016/j.mineng.2012.03.021.
Lee, P.K., Kang, M.J., Jo, H.Y. and Choi, S.H. 2012. Sequential extraction and leaching characteristics of
heavy metals in abandoned tungsten mine tailings sediments. Environ. Earth Sci. 66 1909–1923.
DOI:10.1007/s12665-011-1415-z.
Loock, M.M., Beukes, J.P., Van Zyl, P.G., 2014. A survey of Cr(VI) contamination of surface water in the
proximity of ferrochromium smelters in South Africa. Water SA. 40, 709-716,
doi: 10.4314/wsa.v40i4.16.
Loock-Hattingh, M.M., Beukes, J.P., Van Zyl, P.G. and Tiedt, L.R. 2015. Cr(VI) and Conductivity as
Indicators of Surface Water Pollution from Ferrochrome Production in South Africa: Four Case
Studies. Metall. Mater. Trans. B. 46 2315–2325. DOI:10.1007/s11663-015-0395-x.
Ma, G., Garbers-Craig, A.M. 2006. A review on the characteristics, formation mechanisms and treatment
processes of Cr(VI)-containing pyrometallurgical wastes. The Journal of the Southern African
Institute of Mining and Metallurgy 106 753-763.
Maine, C., Smit, J. and Giesekke, E. 2005. The solid stabilization of soluble wastes generated in the South African
ferrochrome industry, Water Research Commission.
Mandiwana, K.L., Panichev, N., Ngobeni, P., 2007. Electrothermal atomic absorption spectrometric
determination of Cr(VI) during ferrochrome. J. Hazard. Mater. 145, 511-514, doi:
10.1016/j.jhazmat.2007.01.077.
Moskalyk, R.R., Alfantazi, A.M., 2003. Processing of vanadium: a review. Miner. Eng. 16, 793–805,
doi:10.1016/S0892-6875(03)00213-9.
Murthy YR, Tripathy SK, Kumar CR (2011) Chrome ore beneficiation challenges & opportunities – a
review. Minerals Engineering 24(5) 375-380.
Niemelä, P., Krogerus, H., Oikarinen, P., 2004. Proceedings of 10th International Ferroalloys Congress,
Cape Town, South Africa, February 2004, pp. 68-77.
24
NOISH 7605 (2003) Chromium, Hexavalent by Ion Chromatography Method 7605. NIOSH Manual of Analytical
Methods (NMAM).
Oze, C., Bird, D.K., Fendorf, S., 2007. Genesis of hexavalent chromium from natural sources in soil and
groundwater. PNAS, 104, 6544-6549, doi: 10.1073_pnas.0701085104.
Panichev, N., Mabasa, W., Ngobeni, P., Mandiwana, K., Panicheva, S., 2008. The oxidation of Cr(III) to
Cr(VI) in the environment by atmospheric oxygen during the bush fires. J. Hazard. Mater. 153, 937-
941. doi:10.1016/j.jhazmat.2007.09.044
Thomas D.H., Rohrer J.S., Jackson P.E., Pak T., Scott J.N., 2002. Determination of hexavalent chromium at
the level of the California Public Health Goal by ion chromatography. J. Chrom. A956, 255-259.
Tirez, K., Silversmit, G., Bleux, N., Adriaensens, E., Roekens, E., Servaes, K., Vanhoof, C., Vincze, L.,
Berghmans, P., 2011. Determination of hexavalent chromium in ambient air: A story of method
induced Cr(III) oxidation. Atmos. Environ. 45 (2011) 5332-5341, doi:10.1016/j.atmosenv.2011.06.043.
US Environmental Protection Agency (EPA) method 218.6, revision 3.3 (1994) Environmental monitoring
systems laboratory office of research and development U.S. Environmental Protection agency
Cincinnati, Ohio.
Van Staden, Y., Beukes, J.P., Van Zyl, P.G., Du Toit, J.S. and Dawson, N.F. 2014. Characterization and
liberation of chromium from fine ferrochrome waste materials. Miner. Eng. 56 112–120.
DOI:10.1016/j.mineng.2013.11.004.
Venter, A.D., Beukes, J.P., Van Zyl, P.G., Josipovic, M., Jaars, K. and Vakkari, V. 2016 Regional atmospheric
Cr (VI) pollution from the Bushveld Complex, South Africa. Atmos. Pollut. Res. 7 762–767.
DOI:10.1016/j.apr.2016.03.009.
Venter, A.D., Vakkari, V., Beukes, J.P., van Zyl, P.G., Laakso, H., Mabaso, D., Tiitta, P., Josipovic, M.,
Kulmala, M., Pienaar, J.J., Laakso, L., 2012. An air quality assessment in the industrialised western
Bushveld Igneous Complex, South Africa, S. Afr. J. Sci. 108, 1059, doi: 10.4102/sajs.v108i9/10.1059.
Venter, A.D., Van Zyl, P.G., Beukes, J.P., Josipovic, M., Hendriks, J., Vakkari, V. and Laakso, L. 2017.
Atmospheric trace metals measured at a regional background site (Welgegund) in South Africa,
Atmospheric Chemistry and Physics, 17, 4251–4263, www.atmos-chem-phys.net/17/4251/2017/,
doi:10.5194/acp-17-4251-2017
Venter, C. and Liebenberg-Enslin, H. 2004. Air quality impact assessment study for the proposed Xstrata
Lion project, Steelpoort, Report No. APP/04/METAGO-2 Rev 2, Airshed Planning Professionals
(Pty) Ltd, Halfway house, South Africa, October 2004, pp. 1-86.
Xiao, Z. and Laplante, A.R., 2004. Characterizing and recovering the platinum group minerals – a review.
Miner. Eng. 17, 961–979, doi:10.1016/j.mineng.2004.04.001.

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 Pieter Gideon van Zyl
Associated Professor, North-West University
Pieter van Zyl holds a PhD in Chemistry and has extensive experience
scientific research. He is considered an established researcher by the
National Research Foundation. His main interests include atmospheric
chemistry and chrome-related research.
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