Thallium (Tl)

Biol 564
Marine Toxicology
Chia Lin
 Physical and Chemical Properties
 Atomic number 81
 MW = 204.383 g/mol
 Hexagonal crystal structure
 2 oxidation states, Tl+ (forms most stable compounds)
and Tl3+ (resembles Al3+, high oxidizing property)
 25 isotopes (179-210 amu)
 Poor metal
 Relatively lower BP and MP than transitional
metals
 Higher electronegativity
 Softer/malleable
 Exhibits silver/gray in air
 Soon develops to blue-gray (resembles Pb) when left in
air
 Oxides build up

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Use, Application & Prod History
 first isolated by Crookes in 1861
 Occurs naturally in the minerals crookesite, lorandite, hutchinsonite
and pyrites (FeS2)
 obtained as a by-product in the production of H2SO4
 by roasting of pyrite
 by smelting of Pb and Zn ores
 Tl (or thallous salts) is used:
 in the electronics & pharmaceutical industries;
 in optical lenses manufacturing;
 in infrared detectors;
 in roden poisons & insecticides
 Elemental Tl not toxic
 Univalent, Tl (l) and trivalent, Tl (III) salts highly toxic
 Greater toxicity than Pb, Cd, Cu, Hg, Zn in mammals
 Prohibited in 1975 in the U.S. and many countries
 Mode of Entry to Aquatic Env
 A natural constituent in the Earth’s
crust (0.7 mg/kg)
 rare, but widely distributed;
present nearly in all environmental
media
 Associates with K minerals in
clays, soils and granites (not
commercially recoverable)
 Major commercial Tl found in Cu,
Zn, Pb & sulfide ores
 Low concentration in seawater
(constant, 10-15 ng/L), in
unpolluted (5-10 ng/L) and in
polluted freshwater (20-50 ng/L)
 Present in soils
 Sludge from waste water
treatment
 K fertilizers
 Reactivity with H2O
Speciation & Half-life
 Forms thallium hydroxide in the present of H2O
 Soluble enough to be toxic to organisms
 Stable isotopes: 203Tl (29.524 %) and 205Tl (70.476 %)
 Most stable radioisotope: 204Tl
 Half life = 3.78 years
 Biological half-life = 3-8 days
 Tl(I) forms compounds with halogen, oxygen, and sulfur ligands
 similar chemical properties to those of the alkali metal cations
 Tl(III) more toxic than Tl(I)
 The 48-h LC50 values (Daphnia magna)
 Tl(III)NO3- = 24 μg/L
 Tl(III)Cl = 61 μg/L
 Tl(III)CH3COO = 203 μg/L
 aquatic toxicity not affected by water hardness or humic acid
concentration
 Toxicity to aquatic life
 High contents of Tl in surface
water
 Known to kill fish slowly at 1-60
ppm
 Lethal to aquatic insects and
invertebrates at 2-4 ppm
 Lethal to tadpoles at 0.4 ppm
 Affect algae at 0.1 ppm
 In aquatic environments, Tl3+ :
 ~50,000 fold more toxic than Tl+
to the unicellular chlorophyte
 ~34,000 fold more toxic than Cd
ions in aquatic environments
 Toxic effects
 Affects sexual behaviors and reproductive organs in mammals
 Causes damage and changes in the mitochondrial system in
neurons in animals

 Suspected human carcinogen

 Major symptoms from acute (ingest large amounts over a short time)
Tl poisoning include:
 Vomiting, diarrhea, hair loss (temporary)
 Nervous system, lungs, heart, liver, kidneys
 death
 Major symptoms from chronic Tl poisoning include:
 Anorexia, headache, pains in abdomen, upper arms, thighs and in all
over the body
 Blindness and death in extreme cases
 Mode of entry into organisms
 Water, air (inhalation) but low conc.
 Ingestion (major; assimilation by crops)
 Bioaccumulation and biomagnification in aquatic food
webs
 High solubility of Tl(I) compounds
 Absorbed through skin and mucous membranes
 Widely distributed throughout the body
 Accumulates in bones, renal medulla and CNS
 Molecular mode of toxic
interactions
 The exact mechanism of toxicity of Tl not clear
 Possible toxic mechanisms:
 Disrupt/bind to sulfhydril groups of proteins (ligand
formation) & mitochondrial membranes
 inhibiting cellular respiration
 Inhibiting enzymatic reactions and leading to “poisoning”
 Interfere with the function of Na-K ATPase (univalent ions;
similar ionic radii with K+)
 Tl has a 10x higher affinity than K
 Interfere in riboflavin homeostasis
 Forming insoluble complexes
 intracellular sequestration of riboflavin
 Interfere calcium distribution
 Biochemical
Metabolism & Breakdown
 Toxicokinetics of Tl in humans
 First phase: intravascular distribution (last 4 hrs)
 Second phase: distributed into the CNS (4-48 hrs)
 Third phase: elimination (starts after 24 hrs of ingestion)
 Excreted mainly in the urine
 Increased excretion via the kidney due to
 KCl
 Diuretics
 antidotes include (acute Tl poisoning):
 Activated charcoal, British antilewsite (BAL), calcium salts,
cystine, dithiocarb, dithizone, histamine, theophyline, Prussian
Blue (PB, Iron (III) ferrocyanide, ≈10 g)
 Defense strategies / Detoxification
 Chemical ion-exchange, physical adsorption & ion
trapping
 Ion-exchange:
 Tl exchanges with hydrogen from water bound in PB
 With monovalent cations such as Na+, K+, NH4+
 In the gut, PB binds to unabsorbed Tl via:
 Adsorption of ions onto PB
 Trapping within PB
 Interfering with Tl’s enterohepatic circulation,
resulting a reduction in tissue stores
 Binding of Tl to PB in vivo can be influenced by:
 particle size
 Moisture content
 pH
 References
 Hoffman RS. 2003. Thallium toxicity and the role of Prussian Blue in therapy. Toxicol
Rev 22:29-40.
 http://www.speclab.com/elements/thallium.htm
 http://en.wikipedia.org/wiki/Isotopes_of_thallium
 http://en.wikipedia.org/wiki/Thallium
 Hwieh CY, Tsai MH, Ryan DK, Pancorbo OC. 2004. Toxicity of the 13 priority pollutant
metals to Vibrio fisheri in the Microtox® chronic toxicity test. The Science of the Total
Environment 320:37-50.
 Lan C and Lin T. 2005. Acute toxicity of trivalent thallium compounds to Daphnia
magna. Ecotoxicology and Environmental Safety 64:432-435.
 Moore D, House I, Dixon A, Williams G, Volans G, Henry J, Hughes RAC, Cochrane
GM, Atkinson PL. 1993. Thallium poisoning. British Medical Journal 306:1527-1529.
 Peter ALJ and Viraraghavan T. 2005. Thallium: a review of public health and
environmental concenrs. Environmental International 31:493-501.
 Vink BW. 1993. The behavior of thallium in the (sub) surface environment in terms of
Eh and pH. Chem Geol 109:119-123.
 Xiao T, Guha J, Boyle D, Liu C, Zheng B, Wilson GC, Rouleau A, Chen J. 2004.
Naturally occurring thallium: a hidden geoenvironmental health hazard? Environment
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 Yang Y, Faustino PJ, Progar JJ, Brownell CR, sadrieh N, May JC, Leutzinger E, Place
DA, Duffy EP, Yu LX, Khan MA, Lyon RC. 2008. Quantitative determination of
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