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 .

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.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. .

g.Anthropogenic Sources Case Studies: Europe • commercial sources contribute 30 – 60% of the total Cr waste • Domestic sources contribute 20-40%. 1996waste are piled around 20 ) . Car washes as the major potential source. • •    China • On the last two decades: 6million tons of toxic Cr ( Wilkie et al.   e.

 Is Cr important to living organisms BIOLOGICAL FUNCTIONS: GLUCOSE METABOLISM AND OTHERS .

scielo.501 http://www.net/Glossary/chromium-picolinate-.speciation.php?pid=S1517-86922005000500003&script=sci_arttext&tlng=en .br/scielo.Introduction Biological functions: Glucose metabolism and others http://www.

et al.Introduction Biological functions: Glucose metabolism and others (Irwin. R.J. 1997) .

 Where Cr Can be used ANTHROPOGENIC SOURCES .

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

 Wanted dead or alive! CR THE BAD GUY .

edu/~cmallery/150/memb/ion_channel_lg1.miami.bio.jpg .Chromium (VI) is some bad shit Eh. close enough. The true face of Erin Brockovich http://www.

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. 2010 .) 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.

but recent experiments have shown that Mn(VII) has the largest influence Cr ( III ) e. (2010) found that Cr could help to bind As in soil by providing -] more positive binding sites on soil [H2AsO4 particle surfaces . 2010 Al O O O O- K+ Cr 3+ Si Al OOH Hu et al.eMn ( VII ) O “Mn showed to be more efficient in oxidizing Cr(VI) as compared to Fe” – Chaddopadhyay et al.The unsaturated soil environment Mn ( IV ) used to be considered the primary factor for subterranean Cr oxidation.Fe ( III ) e.

(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 .000 Leita et al.The unsaturated soil environment Humic acid: MW ~10.

 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  .

1988) .Pe   Cr(VI) is predominate under the high redox    Cr(III) is predominate under the low redox   (Jerome O. Evert Nieboer. Nriagu.

and CrO42• • HCrO4.------------------- CrO42• PH level Low High H+ concentration high low Dominance species HCrO4CrO42- +H+ .pH Cr((VI))   Dominant species • HCrO4.

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

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. • . particularly in the presence of MnO2 and bacteria. The corresponding oxidation of Cr(III) to Cr(VI) also occurs. However. the kinetics are slow.

which is present everywhere in ground water Robert G. with barium Ba). Mg. K) and alkaline earth (e.Continue  Cr(VI) forms : 1-soluble compounds If it reacts with alkali (e.g.g. 2-soluble salts Otherwise it will form sparingly soluble salt (e. et al.2007) .g. Na. Ca) metal cations.

5 then little or no adsorption will occur Iron hydroxides are considered to be strong adsorbates of Cr(VI) Frederick T. • • If the value of pH is above 8.2004). .Adsorption and complexation: • Cr(VI):the adsorption occurs as a result of chemical reaction between aqueous Cr(VI) species and sites at mineral surfaces. Stanin and Malcolm Pirnie.

Continue  Cr(III):positive charge of Cr(III) ions are attractive to adsorbent surfaces with negative charge.   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. .   The clay minerals (negatively charged) are considered to be very good adsorbents for Cr(III).

as well as fluoride.cyanide. thiocyanate. ammonia .2004) . oxalate and sulfate.Complexation   Cr(VI)   Cr(III)    commonly does not form complexes with inorganic or organic ligands forms complexes with many organic ligands. (LORENZO GIUSTI and SABINE BARAKAT.

 Cr behavior in fresh water CR IN FRESH WATER .

1994 .Chromium in water systems • Originate from natural sources: weathering of rock elements.. • •  • The Chromium concentration in rivers and lakes is typically within the range of 0.  Beaublen et al.5±100 nM although concentrations in polluted environments much higher. dry fallout from the atmosphere and run-off.

precipitation/dissolution and adsorption/desorption reactions. Cr(III) and Cr(VI).Chromium in water systems • • • • • • • • • • • In natural waters. Kieber and Helz. Occurrence & ratio depend on: redox transformation. 1992 . CrO₄². Anoxic conditions. pH & O₂ concentration but nature/concentration of reducers. Oxygenated solutions. Cr(III)/Cr(VI) ratio relies on O₂ concentration. Cr(III) = only form. oxidation mediators and complexing agents. mpanella. 1996.ions should dominate . Intermediary pH. two stable oxidation states. Cr(III) calculated by thermodynamic calculations as the stable species at pH<6 pH>7.

– The majority of Cr(III) complexes become immobilized by macromolecular compounds and taken out of solution. 1994. humic and other acids – This complexing decreases Cr(OH)₃ precipitation at pH conditions present in natural waters.  zynski  and Kieber. hydroxo Cr(III) complexes have a strong tendency to be adsorbed by naturally occurring solids (Rai et al. Rai et al. 1989 . 1989) contributing to a reduction of Cr(III) mobility and bioavailability.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.. – In addition to this.. eg.

1994.     • The main way Cr moves from earth to SW systems is through surface run-off. 1989 .Transport in water ways • Transport in water systems significantly affected by chemical speciation.. Rai et al. the soluble Cr(III) complexed by organic ligands can be conveyed to groundwater and within water systems zynski and Kieber. As well as Cr(VI).

degree of mixing.. 1997 .  • The amount of dissolved Cr river water is decreased during passage through turbid coastal environments (estuarine removal processes)  • Lakes have high biological activity.Lakes and Rivers • Speciation conditions: depth. – organic matter = reductive and complexing agent.  • The transport of metals in rivers is related suspended particles. temperature. redox conditions and quantity of organic matter. a high ratio of sediment to water surface area. which favours Cr(VI) reduction to Cr(III) precipitated or adsorbed into sediment – May be remobilized into the surrounding water  chterberg et al. and dissimilar mixing conditions.

thermal stratification.Seasonally Anoxic Lakes • Complex transport paths arise in seasonally anoxic lakes – In which deep basin water during summer becomes anoxic . 1997 ..biological productivity .     chterberg et al.  • In this type of lake concentration and speciation of Chromium were discovered to fluctuate as a function of depth and season.

• 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 .

R.Cr in Lagoon Water General Background (Irwin. 1997) . et al.J.

R.J.Cr in Lagoon Water Why lagoon/ estuarine water? (Irwin. 1997) . et al.

Lores and Jonathan R. 1997) (Emile M. Pennock.Cr in Lagoon Water What is interesting (Irwin. R. 1998) . et al.J.

 An attempt to understand Cr CASE STUDIES .

Case Studies Paper discussed .

Case Studies Arousa Estuary (North West Spain) (P. Pazos-Capeáns et al. 2010) • Location and Samplin g • Working Frame (20022010) • During Different .

Pazos-Capeáns et al. 2010) .Case Studies Arousa Estuary (North West Spain) • Results: – Redox potential versus pH values obtained in <200 μm Arousa sediments (P.

Pazos-Capeáns et al.Case Studies Arousa Estuary (North West Spain) • Results: – Time evolution of pH and redox potential values in <200 μm sediment samples of Arousa (P. 2010) .

Pazos-Capeáns et al.Case Studies Arousa Estuary (North West Spain) • Results: – Contamination factors of chromium considering every sampling station in all the campaigns in Arousa (P. 2010) .

2010) .Case Studies Arousa Estuary (North West Spain) (P. Pazos-Capeáns et al.

Pazos-Capeáns et al.Case Studies Arousa Estuary (North West Spain) (P. 2010) .

 Cr as a waste… How to deal with this tough guy? CR IN WASTEWATER .

(Motzer. • EPA standards: [Cr] in WW discharge < 0. 2005).1-0. ferrochromium industry. (ICDA.  Wastewater Disposal : chromium metal industry and chemical industry. 2005). stainless steel and chromium alloy industries. • Forms depend mainly on pH and on organic and/or inorganic wastes coming from the industrial processing.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].5 mg/L {other countries: 0. . vMobility Solubility  Influence of pH  Influence of redox (Mohammad Abul Hossain and Mikio Kumita. 2007).5mg/l}    Industrial effluents contain [Cr(VI)] ≈10 to 100mg/L Cr Release by Industry Sector :  Dust or Fume Phase: chromite ore mining.

Chemical Reduction: Adding an electron donor such as S. Precipitation. Fe(II) or Fe(0) (Elisabeth L. Electro-dialysis and Granular Activated Carbon GAC. 2004) . Evaporation. Chemical Reduction. Hawley.Cr in wastewater Cr Treatment in WW and Industrial Disposal • •  Ion exchange. Reverse Osmosis RO.

2000) . aquatic plants. Hexadecylpyridine chloride • • •  NEW  Adsorption Using waste materials as low-cost adsorbents e.g. 2000) . pretreatment is performed to complex the Cr(III) or Cr(VI) by larger molecules e.g. MF or UF membranes.Cr in wastewater Cr Treatment in WW and Industrial Disposal  Membrane Filtration RO membranes operate at higher pressure  NF Thin Film Charged Surface (TFCS) nanofiltration membrane used for Cr(VI) removal.. bagasse fly ash. (Bohdziewicz. al. 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.

C o n clu sio n O h w e m ade i t  Chromium (VI) is a bad xxx  But don’t worry. it can be fixed Any Questions !! .