CHROMIUM, ITS BEHAVIOR AND COMPLEXATIONS IN SOIL AND WATER

Abdullah Dehwah, Ali Zahi, Jake Kinsella, Nicholas Davidson, Samer Al-Mashharawi

Outline
yes! It is going to be a micro century

Introduction Cr in Unsaturated Soil Cr in Groundwater Cr in Fresh Water Cr in Lagoon (Estuarine) Water Cr in Waste Water Conclusion

Mr. Cr, who is he

INTRODUCTION

Introduction
Background about Cr and his family

Introduction
Background about Cr and his family

Where we can find Cr

SOURCES

Introduction
Where is it

Natural Sources
worldwide resources >12 billion metric tons of FeCr2O4 (chromite)
9 5 % i so u th e rn S o u th n A fri ca

I d e p e n d e n t S ta te s, th e P h i i p i e s, a n d o th e r n lp n co u n tri s e

( Testa et al,

Anthropogenic Sources
Case Studies: Europe commercial sources contribute 30 60% of the total Cr waste Domestic sources contribute 20-40%.

e.g. Car washes as the major potential source.

China On the last two decades: 6million tons of toxic Cr ( Wilkie et al, 1996waste are piled around 20 )

Is Cr important to living organisms

BIOLOGICAL FUNCTIONS: GLUCOSE METABOLISM AND OTHERS

Introduction
Biological functions: Glucose metabolism and others

http://www.speciation.net/Glossary/chromium-picolinate-;501 http://www.scielo.br/scielo.php?pid=S1517-86922005000500003&script=sci_arttext&tlng=en

Introduction
Biological functions: Glucose metabolism and others

(Irwin, R.J. et al, 1997)

Where Cr Can be used

ANTHROPOGENIC SOURCES

Introduction
Anthropogenic sources

http://upload.wikimedia.org/wikipedia/commons/7/77/MohawkNiagraFacadeSculpture.jpg http://upload.wikimedia.org/wikipedia/commons/f/f3/Laidlaw_school_bus.jpg

Wanted dead or alive!

CR THE BAD GUY

Chromium (VI) is some bad shit

Eh, close enough.

The true face of Erin Brockovich

http://www.bio.miami.edu/~cmallery/150/memb/ion_channel_lg1.jpg

Chromium (III) potential toxicity

Galacturonic acid

Glucuronic acid

Alginic acid

Cetin et al, 2009

Cr is soil, saturated and unsaturated

THE UNSATURATED SOIL ENVIRONMENT

The unsaturated soil environment

Cr(III) usually found as Cr(OH)3 precipitate or as strongly bound cation Forms a solid monolayer on other metal oxides (particularly Mn) Cr(VI) oxyanions (CrO42- & Cr2O72- ) weakly bound to pH-dependent sites Binding minimal when pH is above PZC of soil particles Primary cause of Cr oxidation is photooxidation at the soil surface

hv

3+ Cr

6+ Cr

Chattopadhyay et al, 2010

The unsaturated soil environment Mn ( IV )

used to be considered the primary factor for subterranean Cr oxidation, but recent experiments have shown that Mn(VII) has the largest influence

Cr ( III )

e- Fe ( III )

e- eMn ( VII )
O

Mn showed to be more efficient in oxidizing Cr(VI) as compared to Fe Chaddopadhyay et al, 2010

Al
O O O

O-

K+ Cr 3+

Si Al

OOH

Hu et al. (2010) found that Cr could help to bind As in soil by providing -] more positive binding sites on soil [H2AsO4 particle surfaces

The unsaturated soil environment

Humic acid: MW ~10,000

Leita et al. (2009) found that humic acid could bind Cr(VI) and would protect it from natural reduction and artificial remediation No sign of change in conformation of acid -X-ray spec No sign of reduction of Cr(VI) during experiment -UV-vis spec

Cr in groundwater aquifers

BEHAVIOR IN GROUND WATER AQUIFERS

Cr Species in ground water

The chromium speciation in ground water depends on two factors: 1-PE( redox potential) 2-pH

Pe
Cr(VI) is predominate under the high redox Cr(III) is predominate under the low redox

(Jerome O. Nriagu, Evert Nieboer,1988)

pH Cr((VI))

Dominant species

HCrO4- and CrO42 HCrO4- ------------------- CrO42

PH level Low High H+ concentration high low Dominance species HCrO4CrO42-

+H+

pH (Cr(III))
Predominant Species Cr(OH)2+ , Cr3+ ,Cr(OH)30 and Cr(OH)4 Cr3+ +H2O------------------------- CrOH2+ + H+ CrOH2+ +H2O-------------------- Cr(OH)2+ + H+
(Jerome O. Nriagu, Evert Nieboer,1988).

Cr(OH)2+ +H2O------------------

Continue
PH level (6-8) low High high(more acidic) low(more alkaline) H+ concentration Dominance species Cr(OH)2+ (CrOH)2+ and Cr3+ Cr(OH)30andCr(OH)4-

Solubility

Bye bye Cr(VI) welcome Cr(III)

Cr(VI) is converted to the less toxic and
much less mobile form of Cr(III) by reduction reactions. The corresponding oxidation of Cr(III) to Cr(VI) also occurs, particularly in the presence of MnO2 and bacteria. However, the kinetics are

slow.

Continue
Cr(VI) forms : 1-soluble compounds If it reacts with alkali (e.g. Na, K) and alkaline earth (e.g. Mg, Ca) metal cations. 2-soluble salts Otherwise it will form sparingly soluble salt (e.g. with barium Ba), which is present everywhere in ground water

Robert G. et al,2007)

Adsorption and complexation:

Cr(VI):the adsorption occurs as a result of chemical reaction between aqueous Cr(VI) species and sites at mineral surfaces.
If the value of pH is above 8.5 then little or no adsorption will occur Iron hydroxides are considered to be strong adsorbates of Cr(VI)

Frederick T. Stanin and Malcolm Pirnie,2004).

Continue
Cr(III):positive charge of Cr(III) ions are
attractive to adsorbent surfaces with negative charge.

The clay minerals (negatively charged) are considered to be very good adsorbents for Cr(III).

Some species of chromium such as chromium(III) hydroxide (Cr(OH)3) is insoluble at site groundwater conditions and will sorb to soil particles and become part of the soil matrix.

Complexation

Cr(VI) Cr(III)

commonly does not form complexes with inorganic or organic ligands forms complexes with many organic ligands, as well as fluoride, ammonia ,cyanide, thiocyanate, oxalate and sulfate.

(LORENZO GIUSTI and SABINE BARAKAT,2004)

Cr behavior in fresh water

CR IN FRESH WATER

Chromium in water systems

Originate from natural sources: weathering of rock elements, dry fallout from the atmosphere and run-off.

The Chromium concentration in rivers and lakes is typically within the range of 0.5100 nM although concentrations in polluted environments much higher.

Beaublen et al., 1994

Chromium in water systems

In natural waters, two stable oxidation states, Cr(III) and Cr(VI). Occurrence & ratio depend on: redox transformation, precipitation/dissolution and adsorption/desorption reactions. Anoxic conditions, Cr(III) = only form. Oxygenated solutions, Cr(III) calculated by thermodynamic calculations as the stable species at pH<6 pH>7, CrO- ions should dominate . Intermediary pH, Cr(III)/Cr(VI) ratio relies on O concentration, pH & O concentration but nature/concentration of reducers, oxidation mediators and complexing agents.

mpanella, 1996, Kieber and Helz, 1992

Chromium in water systems

Cr(III) speciation surface waters shows hydroxo complexes prevailing under circumstances predominant in natural waters

Although Cr(III) can form many diverse complexes with organic materials, eg. humic and other acids
This complexing decreases Cr(OH) precipitation at pH conditions present in natural waters. The majority of Cr(III) complexes become immobilized by macromolecular compounds and taken out of solution. In addition to this, hydroxo Cr(III) complexes have a strong tendency to be adsorbed by naturally occurring solids (Rai et al., 1989) contributing to a reduction of Cr(III) mobility and bioavailability.

zynski and Kieber, 1994, Rai et al., 1989

Transport in water ways

Transport in water systems significantly affected by chemical speciation.

The main way Cr moves from earth to SW systems is through surface run-off. As well as Cr(VI), the soluble Cr(III) complexed by organic ligands can be conveyed to groundwater and within water systems

zynski and Kieber, 1994, Rai et al., 1989

Lakes and Rivers

Speciation conditions: depth, temperature, degree of mixing, redox conditions and quantity of organic matter.

The transport of metals in rivers is related suspended particles.

The amount of dissolved Cr river water is decreased during passage through turbid coastal environments (estuarine removal processes)

Lakes have high biological activity, a high ratio of sediment to water surface area, and dissimilar mixing conditions.
organic matter = reductive and complexing agent, which favours Cr(VI) reduction to Cr(III) precipitated or adsorbed into sediment May be remobilized into the surrounding water

chterberg et al., 1997

Seasonally Anoxic Lakes

Complex transport paths arise in seasonally anoxic lakes
In which deep basin water during summer becomes anoxic - biological productivity - thermal stratification.

In this type of lake concentration and speciation of Chromium were discovered to fluctuate as a function of depth and season.

chterberg et al., 1997

 A decrease in the dissolved Cr concentration between June and September was detected. Furthermore, the Cr(VI) and Cr(III) dominance zones become separated to the

T h i b e h a vi r i co n si n t w i th a t exp e cte d fro m th e se a so n a l s o s ste th i cre a se i te m p e ra tu re , a d e cre a se i p H a n d oxyg e n co n te n t i n n n n th e d e e p e r w a te r ( th e oxyg e n a te d w a te r fa vo u rs C r( V I w h i e th e ) l

How does Cr behave in lagoon (estuarine) water

CR BEHAVIOR IN BRACKISH AND LAGOON (ESTUARINE) WATER

Cr in Lagoon Water
General Background

(Irwin, R.J. et al, 1997)

Cr in Lagoon Water
Why lagoon/ estuarine water?

(Irwin, R.J. et al, 1997)

Cr in Lagoon Water
What is interesting

(Irwin, R.J. et al, 1997) (Emile M. Lores and Jonathan R. Pennock, 1998)

An attempt to understand Cr

CASE STUDIES

Case Studies
Paper discussed

Case Studies
Arousa Estuary (North West Spain)

(P. Pazos-Capens et al, 2010)

Location and Samplin g Working Frame (20022010) During Different

Case Studies
Arousa Estuary (North West Spain)

Results:
Redox potential versus pH values obtained in <200 m Arousa sediments
(P. Pazos-Capens et al, 2010)

Case Studies
Arousa Estuary (North West Spain)

Results:
Time evolution of pH and redox potential values in <200 m sediment samples of Arousa
(P. Pazos-Capens et al, 2010)

Case Studies
Arousa Estuary (North West Spain)

Results:
Contamination factors of chromium considering every sampling station in all the campaigns in Arousa
(P. Pazos-Capens et al, 2010)

Case Studies
Arousa Estuary (North West Spain)

(P. Pazos-Capens et al, 2010)

Case Studies
Arousa Estuary (North West Spain)

(P. Pazos-Capens et al, 2010)

Cr as a waste How to deal with this tough guy?

CR IN WASTEWATER

Cr in wastewater
Cr Behavior in WW and Industrial Disposal
Forms and Standards Industries generate mainly a large amount of (Cr VI) [toxic] and (Cr III) [essential nutrients]. Forms depend mainly on pH and on organic and/or inorganic wastes coming from the industrial processing. EPA standards: [Cr] in WW discharge < 0.5 mg/L {other countries: 0.1-0.5mg/l}

Industrial effluents contain [Cr(VI)]

10 to 100mg/L

Cr Release by Industry Sector : Dust or Fume Phase: chromite ore mining, ferrochromium industry, stainless steel and chromium alloy industries. Wastewater Disposal : chromium metal industry and chemical industry.
vMobility Solubility Influence of pH Influence of redox
(Mohammad Abul Hossain and Mikio Kumita, 2005), (Motzer, 2005), (ICDA, 2007).

Cr in wastewater
Cr Treatment in WW and Industrial Disposal

Ion exchange, Precipitation, Reverse Osmosis RO, Evaporation, Chemical Reduction, Electro-dialysis and Granular Activated Carbon GAC.

Chemical Reduction: Adding an electron donor such as S, Fe(II) or Fe(0)

(Elisabeth L. Hawley, 2004)

Cr in wastewater
Cr Treatment in WW and Industrial Disposal

Membrane Filtration
RO membranes operate at higher pressure NF Thin Film Charged Surface (TFCS) nanoltration membrane used for Cr(VI) removal. MF or UF membranes, pretreatment is performed to complex the Cr(III) or Cr(VI) by larger molecules e.g. Hexadecylpyridine chloride

NEW Adsorption
Using waste materials as low-cost adsorbents e.g. bagasse y ash, aquatic plants, fungi etc Hossainet al Used Black Tea Leaves (UBTLs) has proved to be a low cost and high efficient in removing Cr (VI) in wastewater

Hafiarle et. al., 2000) , (Bohdziewicz, 2000)

C o n clu sio n
O h w e m ade i t

Chromium (VI) is a bad xxx But dont worry, it can be fixed

Any Questions !!