Ajka (Hungary): characterization and potential health effects

of fugitive dust from red mud

Andrs Gelencsr

Andrs Hoffer, Nra Kovts, Beatrix Turczi, gnes Rostsi, Kornlia Imre, Ilona
Nyir-Ksa, dm Tth, Aladr Czitrovszky, Szabolcs Nagy, Attila Nagy, Andrs
cs, Anik Kovcs, rpd Ferincz, Zsuzsanna Hartyni, Mihly Psfai

University of Pannonia, Veszprm, Hungary

This work has been supported by the NKFP grant AEROSOL_EU 2004/3A089 and has appeared in
Environ. Sci. Technol., 45:(4) 1608-1615, 2011.
The Ajka red mud accident, 4th October 2010

- the wall of a red mud pond failed

- 700,000 m3 of highly alkaline (pH12 to 13) red mud suspension was released
- 20 km2 of populated area and fields were inundated by red mud
-10 people died (most drowned, some died later from alkaline burns)
- major damage to property

Major public concerns following the accident

- whats in it? metals? radioactivity? is it only red mud or something else was also
dumped there?
- how to handle, what to do with it?
- will the rest of it remain in the reservoir or another tsunami is possible?
- is inhaled dust dangerous?
- groundwater contamination?
- effect on the Torna stream and the rivers Marcal, Rba, Danube
- effect on soil and agriculture
Problems we addressed

Characterization of the spilled material:

- alkalinity
- bulk chemical and mineralogical composition

Dust formation and its properties:

- resuspension potential
- alkalinity
- size distribution
- grain size, morphology, mineral phase of individual particles
- is the dust any different from the bulk red mud?
- ecotoxicity

Assessment of potential health effects of red mud dust particles

Types of samples

red mud sediment from the ground resuspended PM101 and PM1 aerosol

resuspension potential particle concentration

alkalinity alkalinity
metals mineralogy
mineralogy metals
dust size distribution toxicity
Sampling sites
Sample Description Types of analysis

1 agricultural field covered by red mud XRD, SEM, SD, pH

road covered by red mud crust as a

2 cc, pH
result of traffic
sidewalk covered by thin red mud
3 cc, pH
crust

garden inundated by red mud XRD, XRF, SEM, m/m%

4
driveway inundated by thick mud cc, XRD, XRF, SEM, TEM, SOSChromo,
layer Flash, ICP-OES, pH

red mud crust on road as a result of

5 cc, XRD, SEM
traffic, visible presence of gypsum
driveway inundated by thick mud
6 cc, XRD, SEM, SOSChromo, Flash
layer
Resuspension potential and concentration

- For soils, resuspension is in the 0.01 % range

Resuspension in the lab: (Young et al., Environ. Sci. Technol. 2002, 36,
2484)
PM10 = 0.99 m/m%
- For urban dust ~0.1 % (Martuzevicius et al., 2011
Atmos Environ 45, 310)
PM10-1 mass concentration
24 - 2079 mg m3 - Depends on the available amount of red mud
and its water content
Alkalinity

Sample Alkalinity PM101 (ekv g1)

Kolontr
3.7
(resuspended sediment)

Devecser 1 0.39

Devecser 2 0.77

Devecser 3 3.6

Lower alkalinity in places where neutralized red mud

was redeposited
Size distribution of the resuspended PM10 dust samples

70.0 7.0

60.0 6.0

dW/dlogD (mg m m m )
-1
dN/dlogD (cm m m )
-1

50.0 5.0

-3
-3

40.0 4.0

30.0 3.0

20.0 2.0

10.0 1.0

0.0 0.0
0.01 0.1 1 10
aerodinamikai tmr
aerodynamic diameter (m)
(m m)

Bimodal mass size distribution: Bimodal number size distribution:

~10 m dominated by a peak ~2 m
~4 m
Minerals identified in red mud sediment and dust samples; their likely
origins

Mineral Nominal composition Probable origin

hematite Fe2O3 bauxite
cancrinite Na6CaAl6Si6(CO3)O24 . 2H2O alumina production
hydrogarnet Ca3AlFe(SiO4)(OH)8 alumina production
calcite CaCO3 bauxite or alumina production
perovskite CaTiO3 bauxite
boehmite AlO(OH) bauxite
gibbsite Al(OH)3 alumina production
quartz SiO2 bauxite or soil
albite NaAlSi3O8 soil
muscovite KAl2(AlSi3O10)(OH)2 soil
gypsum CaSO4 . 2H2O clean-up procedure
Mineralogical composition of red mud sediments and PM(101)
samples from XRD
Comparison of bulk particle compositions of red mud sediment and
PM10 dust from X-ray fluorescence spectroscopy analysis

No significant difference between sediment and dust

Fe: slightly more in dust than in the sediment

Ti, V, Cr, Ni: likely substitute for Fe in hematite

Ca, Si: likely smaller concentrations of calcite and quartz in dust

SEM image of the PM(101) fraction of resuspended red mud dust
Typical view of a TEM specimen of the PM1 fraction of resuspended
red mud dust
Particle aggregates dominated by hematite nanocrystals
Summary of mineralogical observations

Mineralogical composition of red mud:

main mineral phases: hematite, cancrinite, hydrogarnet, calcite
there is no distinct difference in mineralogical composition between red mud sediment
and aerosol samples

Elemental composition of red mud:

slight differences between red mud sediment and aerosol samples
minor enrichment of Fe, Ti, Cr, V, Ni in PM101 fraction enhanced amount of
hematite in aerosol dust (metals likely substitute Fe in hematite)

Characters of individual grains:

size: 0.3several m aggregates
various hematite/cancrinite/hydrogarnet ratio in the individual particles
hematite is nanocrystalline
hematite enriched in PM1 dust
Toxicity tests performed

Genotoxicity test (SOS Chromotest):

Mutation the SOS correcting mechanism is activated.

Ecotoxicity test
Test organism: bioluminescent Vibrio fischeri
Normal metabolism light emission luminometer
Toxic substances light emission decreases proportionally to the toxin concentration.
Flash test: developed for the analysis of colored or solid samples.

Previously applied to red mud:

Brunori et al. J. Hazard. Mater. 2005, 117, 55: V. fischeri test
Dauvin Mar. Pollut. Bull. 2010, 60, 197: 10-year-long study of the effects of red mud dumped in the
Mediterranean

Our results: no toxicity

Health effects of inhaled (including Fe-bearing) particles

- size and species both important (the smaller the more dangerous)

- PM2.5 is estimated to cause worldwide

3% of mortality from cardio-pulmonary disease
5% of mortality from cancer of the trachea
10% of mortality from acute respiratory infections

- ultrafine particles are involved in the onset of Alzheimers and Parkinsons

- Fe- and Pb-bearing PM1 particles are often associated with organic carcinogens (mainly
PAHs)

- interactions between Fe-rich particles and epithelial tissue generate free radicals,
causing oxidative damage and changing lung functions

- pneumoconiosis (or siderosis or arc welders lung): roentgenologic changes of the

lungs as a consequence of inhaled iron oxide particles relatively benign form of lung
damage, no sign of cancer

- nanoparticle effects: special properties, new health concern

Potential health effects: alkalinity

NO free alkalinity in the atmosphere

NO public health survey available

Fritschi et al. (2001) J. Occup. Health:

- 2400 employees in alumina refineries
- when exposed to >1 mg m3 caustic
mist: wheeze, rhinitis;
- lung functions did not change

European Chemicals Bureau

NaOH exposure limit 1 mg m-3

At PM10 = 50 mg m-3 (legal ceiling),

7,410-6 mg m-3 NaOH is inhaled
seems insignificant
Potential health effects: resuspension potential

extremely high (nearly 1 m/m%)

the measured flux of resuspended dust was ~200

times higher from thick red mud than from urban road
dust in a city

it can be a problem even if the particles are

themselves not harmful
Potential health effects: particle size
7,00

6,00
Mass size distribution
dM/dlogD (mg m-3 m m-1)
5,00
of red mud dust
4,00

3,00

2,00

1,00
N
0,00
0,01 0,1 1 10
tmr (mm)

alveola
lower tract
upper tract
Mass size
distribution of
urban PM

PM10

PM2.5
Potential health effects: metals

Metal Fugitive dust from red

mud (ppm)

Cu 43
Ni 177
Pb 85
As 63
Cr 341
Ba 66
Potential health effects: metals

Salma et al., 2002

Metal Fugitive dust from red Urban PM (Budapest)

mud (ppm) (ppm)

Cu 43 652
Ni 177 47
Pb 85 1362
As 63 56
Cr 341 128
Ba 66 669
Potential health effects: mineralogy

Calcite:

unlikely to cause adverse health effects

Cancrinite, hydrogarnet:

we are not aware of any studies on health effects

both minerals occur in red mud as platy, lamellar crystals
fibrous habits (as in asbestiform minerals) were not detected

Hematite:

Chen et al. Atmos. Res. 2002, 61, 75:

in an unventilated underground mine (China) with heavy exposure to radon, quartz
dust and diesel fumes hematite miners had a significant excess risk of non-
malignant respiratory disease and lung cancer

Lawler et al. J. Occup. Med. 1985, 27, 507:

hematite miners not exposed to significant radon concentrations, smoking was
prohibited and diesel emission was absent no apparent health risks associated
with hematite mining
Potential health effects: hematite nanoparticles

Auffan et al. Nature Nanotechnology 2009, 4, 634:

Fe(0) and Fe(II) was found toxic for E. coli, whereas Fe(III) (hematite) was
not toxic

Karlsson et al. Toxicology Letters 2009, 188, 112:

magnetite and hematite nanoparticles showed no or very small cytotoxicity

Bhattacharya et al. Particle and Fibre Toxicology 2009, 6:

hematite nanocrystals induced DNA breakage in human lung cells

however, the material was not properly characterized and was likely not
hematite
Particulate matter in the air
of a Budapest underground
metro station

character of PM similar to red

mud dust
concentration: 130170 mg/m3
size distribution similar to that of
red mud dust
mainly aggregates of hematite
nanocrystals
enrichment of Mn, Ni, Cu, and Cr
several hundred thousands
people exposed to it daily

Salma et al. 2009 Atmos Environ 43, 3460 hematite hematite+magnetite

Summary: how dangerous is red mud dust compared to
urban dust?

in red mud dust submicron particles are practically absent, in contrast to urban dust
that contains an ultrafine mode in the size distribution

there is no reason to think that any of the mineral components of red mud could
cause cancer or other serious disease; in contrast, urban aerosol is loaded with
nanosized soot and metal particles with associated PAHs and organic nitrates

metal concentrations not higher than in urban aerosol, and most metals appear to be
in stable crystal structures;

no toxicity was measured for red mud dust; in contrast, the same tests showed
variable toxicity for urban aerosol

Red mud dust appears to be less hazardous than urban particulate matter
of the same concentration
Some words of caution

Extraordinary resuspension potential under unfavorable conditions

extremely high concentrations of PM10 as in dusty workplaces

At very high concentrations even inert dust may be harmful

Since the red mud affected residential areas, elderly people, children and
people suffering from chronic diseases are also exposed to it

It is therefore justified to clean up the red mud from residential

areas and to prevent its resuspension from fields.
People involved in moving dry red mud should wear face masks.