Lecture 8 Radioactive Isotopes Definitions and types of decay Derivation of decay equations Half lives and mean lives Secular Equilibrium Useful radiotracers in oceanography E & H Chpt 5

The chart of the nuclides - decay Q. 230Th90 How many protons / neutrons?

Full Chart of the Nuclides Valley of Stability 1:1 line For 230Th N/P = 1.55

Radioisotopes and decay Definitions and Units Parent – Original radioactive atom Daughter – The product of decay Decay Chain – A series of sequential decays from one initial parent Decay is independent of chemistry and T and P. Decay is only a property of the nucleus (see Chart of Nuclides) Types of Decay DP DN DAtomic Wt. Alpha a He2+ -2 -2 -4 Beta b e- + 1 -1 0 (n → P+ + e-) Gamma g “packets of excess energy” Measurements

The chart of the nuclides – decay pathways b decay X X a decay

Mathematical Formulation of Decay Decay Activity (A) = decays per time (e.g. minutes (dpm) or second (dps)) A = l N l = decay constant (t-1) N = # of atoms or concentration (atoms l-1) Remember 1 mol = 6.02 x 1023 atoms Units: Becquerel (Bq) = 1 dps (the official SI unit) Curie (Ci) = 3.7 x 1010 Bq = Activity of 1 gram of 226Ra Named after Pierre Curie See this link for the history: http://www.orau.org/ptp/articlesstories/thecurie.htm

Decay Equations (essential math lessons) Decay is proportional to the # of atoms present (first order) dN/dt = - N = AN where N = the number of atoms of the radioactive substance present at time t  = the first order decay constant (time-1) The number of parent atoms at any time t can be calculated as follows. The decay equation can be rearranged and integrated over a time interval. where No is the number of parent atoms present at time zero. Integration leads to or or

Decay Curve Both N and A decrease exponentially

Half Life The half life is defined as the time required for half of the atoms initially present to decay. After one half life: From the decay equation =  t1/2 ln (2) =  t1/2 0.693 =  t1/2 so Math note: -ln(1/2) = - (ln 1 – ln 2) = - ( 0 – ln 2) = + ln2 = 0.693

Mean Life = Average Life of an Atom = 1 / l = (1/0.693) t1/2 t = 1.44 t1/2 Q. Why is the mean life longer than the half life?

Isotopes used in Oceanography steady state transient U-Th series are shown on the next page. These tracers have a range of chemistries and half lives. Very useful for applications in oceanography.

Two forms of Helium 3He2 from beta decay of 3H1 (called tritium) and primordial from the mantle 3H1 = 3He2 + b 4He2 the product of alpha decay from many elements (especially in U-Th series) How would you expect their distributions to vary in the ocean?

Example distributions of 3He from mid-ocean ridge crest John Lupton (NOAA) et al (various)

Q. Why is the inside of the earth hot? Q. What is the age of the earth? 6000 years or 4.5 x 109 years

238U decay products in the ocean U – conservative Th – particle reactive Ra – intermediate (like Ca) Rn = conservative Pb – particle reactive Q. What controls the concentration of 238U in SW?

Parent-Daughter Relationships Radioactive Parent (A) Stable Daughter (B) A → B e.g. 14C → 15N (stable) Production of Daughter = Decay of Parent 2-box model l A A B Example: 14C → 15N (stable) t1/2 = 5730 years l = 0.693 / t1/2

Radioactive Parent (A) Radioactive Daughter (B) A → B → 2-box model lA lB A l A B l B source sink mass balance for B solution: solution after assuming NB = 0 at t = 0

Three Limiting Cases 1) t1/2(A) > t1/2(B) or lA < lB one important example: 2) t1/2(A) = t1/2(B) or lA = lB e.g. 226Ra → 222Rn 3) t1/2(A) < t1/2(B) or lA > lB 1600yrs 3.8 days Case #1: long half life of parent = small decay constant of parent SECULAR EQUILIBRIUM Activity of daughter equals activity of parent! Are concentrations also equal???

Q. Are concentrations also equal??? Example: 226Ra and 222Rn

Secular equilibrium (hypothetical) t1/2 daughter = 0.8 hr t1/2 parent =  Total Activity (parent+daughter) Parent doesn’t change ★ Activity of parent and daughter equal at secular equilibrium daughter Activity (log scale) ★ ! Daughter grows in with half life of the daughter! t1/2 5 x t1/2 time (hr)

Example: Grow in of 222Rn from 226Ra After 5 half lives Another way to plot After 5 half lives activity of daughter = 95% of activity of parent

Example: Rate of grow in Assume we have a really big wind storm over the ocean so that all the inert gas 222Rn is stripped out of the surface ocean by gas exchange. The activity of the parent of 222Rn, 226Ra, is not affected by the wind. Then the wind stops and 222Rn starts to increase (grows in) due to decay. Q. How many half lives will it take for the activity of 222Rn to equal 50% (and then 95%) of the 226Ra present? Answer: Use the following equation to calculate the activity A at time t

Radon is a health hazzard! Radon source strength from rocks Why are some zones high (red)?

There is considerable exposure due to artificially produced sources! Possibly largest contributor is tobacco which contains radioactive 210Po which emits 5.3 MeV a particles with an half life of T1/2=138.4days.

Was Litvinenko (a former Russian spy) killed by 210Po Was Litvinenko (a former Russian spy) killed by 210Po?? A case study of 210Po Toxicity of Polonium 210 Weight-for-weight, polonium's toxicity is around 106 times greater than hydrogen cyanide (50 ng for Po-210 vs 50 mg for hydrogen cyanide). The main hazard is its intense radioactivity (as an alpha emitter), which makes it very difficult to handle safely - one gram of Po will self-heat to a temperature of around 500°C. It is also chemically toxic (with poisoning effects analogous with tellurium). Even in microgram amounts, handling 210Po is extremely dangerous, requiring specialized equipment and strict handling procedures. Alpha particles emitted by polonium will damage organic tissue easily if polonium is ingested, inhaled, or absorbed (though they do not penetrate the epidermis and hence are not hazardous if the polonium is outside the body). Acute effects The lethal dose (LD50) for acute radiation exposure is generally about 4.5 Sv. (Sv = Sievert which is a unit of dose equivalent). The committed effective dose equivalent 210Po is 0.51 µSv/Bq if ingested, and 2.5 µSv/Bq if inhaled. Since 210Po has an activity of 166 TBq per gram (1 gram produces 166×1012 decays per second), a fatal 4-Sv dose can be caused by ingesting 8.8 MBq (238 microcurie), about 50 nanograms (ng), or inhaling 1.8 MBq (48 microcurie), about 10 ng. One gram of 210Po could thus in theory poison 100 million people of which 50 million would die (LD50).

Body burden limit The maximum allowable body burden for ingested polonium is only 1,100 Bq (0.03 microcurie), which is equivalent to a particle weighing only 6.8 picograms. The maximum permissible concentration for airborne soluble polonium compounds is about 10 Bq/m3 (2.7 × 10-10 µCi/cm3). The biological half-life of polonium in humans is 30 to 50 days. The target organs for polonium in humans are the spleen and liver. As the spleen (150 g) and the liver (1.3 to 3 kg) are much smaller than the rest of the body, if the polonium is concentrated in these vital organs, it is a greater threat to life than the dose which would be suffered (on average) by the whole body if it were spread evenly throughout the body, in the same way as cesium or tritium. Notably, the murder of Alexander Litvinenko in 2006 was announced as due to 210Po poisoning. Generally, 210Po is most lethal when it is ingested. Litvinenko was probably the first person ever to die of the acute α-radiation effects of 210Po , although Irene Joliot-Curie was actually the first person ever to die from the radiation effects of polonium (due to a single intake) in the late 1950s. It is reasonable to assume that many people have died as a result of lung cancer caused by the alpha emission of polonium present in their lungs, either as a radon daughter or from tobacco smoke.

Fukushimi Nuclear Disaster - overview http://www.dailykos.com/stories/2016/3/11/1499964/-Fukushima-s-Impact-on-North-America-Tsunami-debris-invasive-species-and-radionuclides?_=2016-03-11T18%3A04%3A41-08%3A00 https://soundcloud.com/cbcvictoria/an-update-on-fukushima-radiation-from-oceanographer-jay-cullen?utm_source=soundcloud&utm_campaign=share&utm_medium=facebook

Schematic Scavenging Model

We build upon a one-dimensional reversible scavenging model (Bacon and Anderson, 1982) to provide a measure of scavenging intensity from the observed distribution of dissolved 230Th. The residence time of dissolved 230Th in the deep ocean (20 - 40 years, Hayes et al., 2013b) is sufficiently small that the dissolved 230Th profile at most locations, and especially in central ocean gyres, is relatively insensitive to lateral exchange processes. Instead, the dissolved 230Th profile responds almost entirely to local scavenging intensity. Neglecting lateral supply or removal, the reversible scavenging model predicts a linear increase with depth (z) for the concentration of dissolved (Cd ) and particulate (Cp ) phases of particle reactive tracers produced in situ . dCp/dZ = P/S and dCd/dZ = P/SK For those elements for which particulate excess (adsorbed) trace element concentrations (xsMe) can be evaluated, we will provide a measure of scavenging intensity, expressed in terms of scavenging residence time (τMe ), as: τMe = τTh • Kd (Me)/Kd (Th) (Bacon and Anderson, 1982), where τTh is the residence time of Th, evaluated as described above, and Kd is the partition coefficient, defined as moles of particulate xsMe (or 230 Th) per gram of particles divided by moles of dissolved Me (230 Th) per gram of seawater. Kd is equivalent to K (concentration ratio defined above) divided by the mass concentration of particulate matter.

A) Idealized profiles of dissolved 230 Th calculated for a 3-fold range of scavenging intensities (SK). B) Measured dissolved 230 Th profiles at three representative stations in the Subarctic North Pacific (SNP, solid dots) together with profiles from the Hawaii Ocean Time Series station ALOHA (22°45’N 158°W) and the SAFe station (40°N 140°W) in the North Pacific Subtropical Gyre (NPSG, gray triangles and dots, respectively). C) Dissolved 231 Pa profiles at the same stations as in (B). Panels (B) and (C) are from (Hayes et al., 2013b). ALOHA data are from (Francois, 2007).

The three models to be considered are summarized below. Model I: Irreversible uptake Th (dissolved)-• Th (particulate) Model II: Irreversible uptake with fast-particle removal Th (dissolved)•, Tt•(particulate)-• Th (fast particle) Model III: Reversible exchange Th (dissolved).•--•->• Th (particulate) k- 1

Top: Cruise track and station numbers for the US GEOTRACES Eastern Pacific Zonal Transect (EPZT). Bottom: EPZT section of dissolved Fe, complements of P. Sedwick and B. Sohst. Superimposed on the Fe section are concentration profiles of dissolved 230 Th at Stations 25 and 30 (locations indicated by white arrows). Although the dissolved 230Th profiles are from different locations, they are plotted on a common concentration axis for clarity. To convert from dpm/m3 to fg/kg, multiply by 21.9.

A) Concentration profiles of dissolved and total (sum of dissolved and particulate concentrations, the variables actually measured) 230Th at EPZT Station 25 are compared to the dissolved 230Th profile from the SAFe station in the Subtropical North Pacific Gyre to illustrate the magnitude of 230Th depletion at the depth of the hydrothermal plume (~2500 m). B) Activity ratio of particulate xs231Pa/xs230Th on particles collected by in situ filtration at EPZT Stations 25 and 30. Concentration units in 9A differ from those in Figure 7. To convert from dpm/m3 to fg/kg, multiply by 21.9 for 230Th.