Light in the Ocean .. and its influence on photochemistry Light travels faster than sound. This is why some people appear bright - until you hear them speak. Disclaimer – quote probably not attributed to Einstein Light is a form of electromagnetic radiation – with wave-like properties wavelength (λ) = C/ ν where λ is the wavelength in meters, C is the speed of light in a vacuum (3 x 108 m s-1) and ν is the wave frequency (# of wave crests (cycles) per second) Electromagnetic energy travels in distinct packets called photons. The energy in each photon is given by: E = h where h is Planck’s constant (6.63 x 10-34 J s) and ν is the frequency (s-1). Since ν = C/ λ we can relate energy to wavelength: E = hC/ λ Thus, the energy in a photon is inversely proportional to the wavelength (longer λ = less energy; shorter λ = more energy) Units used during measurements of light Einstein = 6.02 x 1023 photons i.e. 1 mole of photons It is convenient to work with Ein since photochemistry is a quantum process (if the quantum yield is 1, then one mole of photons causes 1 mole of molecules to react) Light photon flux – often given as μEin cm-2 s-1. Photosynthetically active radiation (PAR) is often given in these units; A bright summer day has a solar photon flux of about 2500 μEin cm-2 s-1 (= 2500 μmol photons cm-2 s-1) The rate of light Energy delivery is often given in Watts 1 Watt (W) = 1 Joule second-1 Light energy flux is given in W m-2 Wavelength-specific energy is often specified. That is, the energy at a certain λ (or from a range of λ i.e. PAR (400-700 nm)) Energy per mole of photons at specific wavelengths Energy per photon at specific wavelengths 8E-19 Joules per photon 7E-19 UV-R Visible 6E-19 5E-19 4E-19 InfraRed 3E-19 Photosynthetically-Active Radiation (PAR) is ~400-700 nM 2E-19 1E-19 0 280 400 nm 380 480 580 680 780 wavelength (nm) Short wavelength light (i.e. UV) has higher energy per photon! UV-R Visible light Most incident solar energy is in the visible band! No UV-C reaches Earth’s surface From Whitehead et al, 2000 Light penetration into the ocean Light energy is absorbed in seawater such that total light energy (irradiance) at a given wavelength decreases exponentially with depth into the water Total light energy Iz = irradiance at depth z Io = irradiance at surface Kd = attenuation coefficient (m-1) Depth (z) Kd is the fraction absorbed per meter Iz = Io e-K d z There will be a different Kd for each wavelength! What happens to this light energy? Absorbed Energy Iz/Io (fraction of surface irradiance) Large Kd rapid extinction & shallow penetration λ1 λ2 λ3 Depth Small Kd - slow extinction with depth & deep penetration Light absorption (i.e. Kd,λ) will be affected by several factors – more later…. Within the visible bands, red wavelengths are absorbed rapidly with depth. Blue wavelengths generally penetrate the deepest. The penetration of visible light (PAR) depends on the characteristics of the water, including phytoplankton abundance. Spectral irradiance at depth in the ocean is measured by spectral radiometers Spectral radiometer data for optically-clear water from the central Gulf of Mexico 0 Low UV wavelengths are attenuated rapidly with depth. Greater than 90% of UV-B (< 320 nm) is absorbed above 15-20 m. 5 305 nm 10 320 nm 340 nm 15 380 nm 20 25 PAR 30 0 20 40 60 Total energy in 400-700 nm band The 1% PAR depth at this site was ~120 m 80 100 % of surface irradiance 120 UV absorption properties vary among water masses 305 This is equal to the 10% irradiance depth From Whitehead et al, 2000 1% light depth for any wavelength is given by 4.6/Kd That is Iz/Io = e-Kz or ln(Iz/Io) = -Kdz ln(0.01) = -Kdz or 4.6/Kd= z1% DOM is the main chromophore (absorber of light) in the ocean. More correctly, it is specific constituents of the DOM that are the chromophores. Together these organic chromophores constitute the Colored Dissolved Organic Matter (CDOM) (also called chromophoric DOM) CDOM (at high concentration) can give water a yellow color (Gelbstoffe) and a high optical absorbance, particularly in the UV part of the spectrum. Tea colored, black-water rivers are very high in CDOM! Absorption coefficient (m-1) Total 0.8 0.6 Light absorption by seawater is mainly by DOM! DOM Absorption spectra for whole water, and the DOM, particulate matter, and pure water fractions for a coastal seawater sample from the mid Atlantic Bight. 0.4 0.2 particles Water 0.0 300 350 400 450 Wavelength (nm) 500 550 From DeGrandpre et al, 1996 Differences in light absorption/attenuation in different water masses is governed mainly by: Particles – organic and inorganic DOM - quantity and quality Influenced by primary production and proximity to rivers and sediments The optical absorbance of water is usually directly related to the DOC (and DOM) concentration – but this Abs 350 nm relationship varies from one water mass to another. River water Shelf water Ocean water With exposure to UV-R, CDOM becomes bleached and it losses its absorbance, thereby changing the A350 vs. DOC relationship DOC conc. Seawater CDOM absorption coefficient for 370 nm light as a function of Chl a concentration in those same waters Chlorophyll a (mg m-3) This study found that seawater absorption coefficients in these hyper-oligotrophic waters were lower than published values for pure water! Photochemistry Photochemistry affects: Photosynthesis & Bacterial growth (photobiology) Biological reactivity of DOM (both increasing and decreasing its lability) Molecular weight distribution of DOM Mineralization (loss) of DOM Production of CO2(aq) from DOM Metal cycling and availability – via photoreduction etc. Pollutant degradation When photon (light) energy is absorbed by molecules, a variety of things can happen. • Electrons transiently jump to higher orbitals, then spontaneously fall to their original position (times scales of nanoseconds). This results in fluorescence with emission being longer than the of the photon absorbed (the excitation photon) • Molecule becomes “excited” and more reactive A --> A* • Molecule becomes oxidized (loses electron to a receptor) • Molecule becomes reduced (steals electron from a donor) Primary vs. Secondary Photochemistry For a primary process, compound A absorbs light energy directly and is converted into terminal products: hν AB+C For a secondary reaction, A absorbs light energy and becomes excited – but it then transfers the energy to a receiving molecule B, forming excited-state B*. This can go on and on … In this case, A hν A A* + B B* + A’ chain reactions Where A* and B* are excited state species Example: DMS does not absorb light directly so no primary photolysis. DMS oxidation in the light, occurs via a photosensitizer (e.g. DOM or NO3-). functions as a photosensitizer - it absorbs light energy and then causes something else to react. Molecular oxygen is a major reactant in photochemical reactions (though it doesn’t absorb light directly). If O2 reacts with excited molecule, highly reactive singlet O2 (1O2) can form If a photoactive molecule absorbs a photon and donates e- to O2, it yields superoxide anion (O2-) a reduced form of oxygen that is highly reactive. Superoxide can be converted to hydrogen peroxide (H2O2), either chemically or enzymatically (superoxide dismutase does this). H2O2 is also a strong oxidant and reactive form of oxygen. H2O2 can undergo direct photolysis (with UV-R) or can react with Fe(II) to form OH radicals (OH), one of the most potent oxidants known. All these reactive oxygen species are formed in seawater via photochemical reactions! Inorganic constituents in seawater are not generally photoreactive. Several notable exceptions include: Nitrate 319 - 333 nm NO3- + H2O + light NO2- + •OH + OHNitrite 325 - 380 nm NO2- + H2O + light NO + •OH + OH- OH radicals are about the most potent oxidants known! The specific photo-reactivity (per mole) of nitrite is much greater than for nitrate Polar seas have Concentrations in Antarctic surface waters Nitrate 15-30 µM Nitrite 0.1 – 0.2 µM Nitrate and nitrite can range from 1-15 µM in temperate waters, mainly in winter and spring. Even higher concentrations can be found in coastal waters & river plumes very high nitrate concentrations! This has implications for photochemisty & biology Transition metals such as Fe, Mn & Cu have primary photochemistry hν More labile and biologicallyavailable Fe(III) Fe(II) Percent contribution of different wavelength bands of solar radiation to photoreduction of Fe(III) colloids in Antarctic waters Surface irradiance UV-A (320-400 nm) Depth integrated in water column >60% 55% Visible (400-700 nm) 30% 40% UV-B (290-320 nm) 3.5 – 6.5% 1.8 – 3.0% From Rijkenberg et al. 2005. GRL Photoreduction (direct & photosensitized) is important in maintaining metals in surface waters and keeping some of the metal pool available to phytoplankton Influence of photochemistry on organic compounds • Mainly driven by UV-R • DOM (i.e. CDOM) is the main absorber of UV-R in seawater • UV-R absorption by CDOM causes alteration of DOM hν CDOM Altered CDOM + photoproducts CO2 CO After Kieber Mopper Miller Moran etc Photodegradation also bleaches CDOM, decreasing its absorption and its photoreactivity COS H 2 O2 Low molecular weight organic compounds e.g. formaldehyde, glyoxylate, etc. (i.e. labile to bacteria!) Moran and Zepp, 1997, L&O From Mopper and Kieber, 2000 Photooxidation as a major sink for refractory DOM in the sea Photochemical Blast Zone - some DOM oxidized Upwelling of refractory, old DOM NADW formation. Labile DOM is utilized in relatively short time - leaving old refractory carbon to make another circuit Deep water transit (= 1000 y) Little alteration of old, refractory carbon If ultra-refractory DOM has average age of 6000 years, and if ocean circulation time is 1000 y, then on average 16.7% of this old carbon will be lost each circulation cycle. Summary of Important photolabile compounds in seawater Compounds which are photolabile Products Nitrate (NO3-) •OH, NO2- Nitrite (NO2-) •OH, NO? Fe3+ Fe2+ DOM-humic substances Anthropogenic pollutants H2O2, Low molecular weight acids and aldehydes, CO, CO2, COS Modified pollutants DMS (dimethylsulfide) DMSO and other products Optical Buoy - In situ incubations in natural light field 0 Quartz tubes 5 305 nm 10 320 nm 340 nm Incubated water experiences natural light field 15 380 nm 20 25 PAR 30 0 20 40 60 80 100 % of surface irradiance 120 Comparison of Photochemical and Biological DMS loss processes – Ross Sea Polynya, Terra Nova Bay - January 13, 2005 -1 DMS consumption rate constant (d ) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0 In situ irradiation 5 Photolysis 10 Depth (m) MLD 15 Bio consumption from CTD samples 20 25 30 35 Conditions: Photolysis Bio consumption Shallow mixing, calm winds, cloudy am, sunny pm. How are the biological processes affected by exposure depth (UV radiation)? -1 -1 Bacterial production (nM Leu d ) DMSPd consumption (nM d ) Irradiation depth (m) 0.0 0.5 1.0 1.5 DMS consumption (nM d-1) 0 2 4 6 8 10 12 14 16 18 2.0 0 0 0 0 5 5 5 10 10 10 15 15 15 20 20 25 25 30 30 20 25 30 In situ irradiation Array Dark 2 4 6 8 10 12 Mixing Depth governs exposure of surface plankton to PAR and UV-R Hypothetical UV-R penetration Deep Mixing Mixing depth also affects surface nutrient regime and distribution of key phytoplankton e.g. N-fixers Shallow Mixing 0 MLD = 50m MLD = 25m 25 Depth (m) UV Shade 50 75 100 Deep mixing gives lower dosage to surface plankton - allows recovery/repair from UV damage t Shallow mixing results in higher UV dosage for surface plankton, with less recovery time t Using Solar UV to disinfect drinking water National Geographic, April, 2010 Our changing atmosphere – stratospheric ozone depletion and the increase of UV-radiation at the Earth’s surface Stratospheric ozone depletion is causing UV-R to going up everywhere on Earth • Highest total solar energy and highest total UV energy are at the equator. • Largest seasonal variability in UV-R occurs at high latitudes- like the Arctic and Antarctic. The ozone hole over Antarctica enhances flux of UV-B at the sea surface Spectral shift in energy under ozone hole conditions Ozone in the atmosphere is measured in Dobson Units (DU). Data from Palmer Station, 1993 Marine organisms are very sensitive to UV-B radiation! Dave Kieber How does UV-R affect biology (and hence chemistry) in the surface ocean? Inhibition of photosynthesis Inhibition of bacterial production and growth Selection force for UV-resistant organisms, and those able to adapt by production of UV screens (i.e. Mycosporine amino acids) Possible mutagen driving evolution? Factor affecting viability of eggs and larvae of macroorganisms that reside in surface waters? Possible synergism with pollutants (e.g. PAH’s) End Metals (e.g. Fe, Mn) held in organic complexes including • Humics • EDTA • Siderophores are photolabile – resulting in photoreduction of metal and oxidation of the organic molecule. This type of photosensitized metal photoreduction is more important than primary photo-reduction of the metals. Photoreduction (direct & photosensitized) is important in maintaining metals in surface waters and keeping some of the metal pool available to phytoplankton The absorption of light is a quantum process Φ = quantum yield = # of reactions / # of photons absorbed The rate of a photochemical reaction of A is given by: dA AI A dt Quantum yield Only when light is absorbed can photochemical reactions occur – if compounds are transparent to light, then no photo reactions occur Specific absorption of actinic radiation – light absorbed per unit volume of water per unit time Actinic = chemically-active radiation If the concentration of the actual chromophore is not known, the apparent quantum yield (ΦA ) is reported. The ΦA for seawater reactions is usually << 1 (few reactions per photon absorbed) The quantum yield for marine photochemical reactions is often much less than 1. For example, the quantum yields of H2O2 photoproduction range from 0.00003 to 0.001. Quantum yields also tend to decrease at longer wavelengths (less energy per photon). Figure from Moran and Zepp, 1997 Open symbols are seawater Absorption of light in the sea > 95% of light energy reaching the ocean surface enters the water if > 20o. 5-7% of light that enters ocean is lost due to backscatter (water leaving radiance) reflection Absorption 5-7 % backscatter About 50% of absorbed radiation is infrared which heats the water. Total attenuation of light in aquatic systems K= Total attenuation aw Absorbance by water molecules + ap + ao Absorbance Absorbance by particles by organics + ai + Absorbance by inorganic molecules Sw + Scattering by water Sp Scattering by particles Absorbance means light energy is absorbed by chemicals in the system. Molecules that absorb light are called chromophores Practical considerations for UV-research Optical properties of various lab materials Optical quartz – transparent to virtually all wavelengths Borosilicate glass (e.g. Pyrex, Kimax, Duran) - (variable – can cut off < 340 nm) Teflon (FEP) – Transparent to most UV- but some scattering Polycarbonate (cuts off < 340 nm) Whirlpak polyethylene bags - Transparent to UV-R – convenient to use, but must check for contamination Acrylics – different optical properties depending on type (see next slide) Selective filtration of light wavelengths Plexiglas-G – cuts off < 370 nm Mylar-D – cuts off < 315 nm (i.e. UV-B) Mylar D and UF-3 acrylic % Transmittance 100 90 % transmittance UF-3 (or UV-O) acrylic – cuts off < 400 nm (i.e. all UVR) 80 70 60 50 40 30 Mylar-D 20 UF-3 Acrylic 10 0 270 300 330 360 390 420 450 480 510 540 570 600 Wavelength (nM) The ozone hole over Antarctica increased through 2005 – letting in more ultraviolet B radiation 2004 Total Ozone Mapping Satelite (TOMS) ftp://jwocky.gsfc.nasa.gov/pub/eptoms/images/spole/Y2004/ Stratospheric ozone depletion affects the total flux of ultraviolet radiation (UVR) to the Earth’s surface, but has a bigger impact on UVB fluxes. Natural ozone in the stratosphere absorbs UV-B radiation (290-320 nm) The protective layer is being destroyed by man-made chlorofluorocarbons (CFC’s) Natural sources of halocarbons (i.e. methyl bromide) also play a role in ozone destruction Action Spectra - For photochemical reactions, the rate of reaction is a function of wavelength Sunlight normalized action spectrum Action spectrum Rate of DMS photolysis Rate of DMS photolysis per photon 290 In daylight Wavelength (nm) 400 290 More photons in UV-A Peak activity near 350 nm Wavelength (nm) (the type of dependency is governed by the light absorbance of the material or system) 400 Bouillon & Miller, GRL 2004 DMS photolysis is mainly driven by UV wavelengths Apparent quantum yield DMS loss (%) 100 10 m 150m 80 60 65% of photolysis caused by UV-A 40 35% by UV-B 20 Toole et al., GRL 2004 0 Full 305 320 345 380 395 Dark Optical Cut-off Filter (nm) (Toole et al., GRL 2004) About 35% of the DMS photolysis attributed to NO3- Nitrite (M) 0 1 2 3 4 5 100 DMS loss (%) High DMS photolysis rates in Southern Ocean waters are partially due to natural high nitrate concentrations A 80 +Nitrate 60 40 +Nitrite 20 0 The remaining 65% of photolysis was due to highly reactive CDOM 0 100 200 300 400 500 Nitrate (M) 2.0 B k (h-1) 1.6 1.2 Natural NO3conc. 0.8 0.4 Added NO3- 0.0 0 100 200 300 400 Nitrate (M) 500 Influence of NO3- on DMS photochemistry also documented in the sub-Arctic Pacific during an Fe-fertilized phytoplankton bloom NO3- drawdown in patch Decreasing DMS photolysis rate constant with time Bouillon and Miller, (GRL, 2004) Photolysis rate given here as apparent quantum yield (AQY) at 330 nm. NO3drawdown in bloom Photolysis dominated DMS loss processes at the ice edge station, during pre-bloom conditions. Data from Toole et al. 2004 GRL Rate constants for depth-integrated water column DMS loss processes at station M (Nov 11 &13, 2003). Process rate constant (d-1) Sea-air exchange 0.023 Biological consumption 0.083 - 0.20 Photolysis 0.5 - 0.71 Summary of DMS photolysis in high latitude, nitrate-rich waters • Toole et al., 2004 results – high photolysis rates in pre-bloom Southern Ocean waters compared to other ocean locations– partly due to nitrate, but also high CDOM reactivity • Photolysis was major loss process in ice edge waters where bio and ventilation loss was low • Mechanism still unknown – Bouillon (OH radicals vs. Toole (not just OH) • DMSO yield from DMS photolysis ranged from 33-45% in pre-bloom waters Strong absorption Weak absorption Strong absorption Surface irradiance Downwelling spectral irradiance Irradiance at depths indicated Strong absorption means rapid attenuation with depth UVR PAR Adapted from: Smith et al. 1992. Ozone depletion: UV radiation and plankton biology in Antarctic waters. Science 255: 952 PAR UV energy, as % of total, decreases with greater sun angle Larger zenith angle means longer path through atmosphere, and hence more UV absorption 79o Infrared Earth atmosphere From Whitehead et al, 2000 0o zenith angle The quartz tube parade Quartz tube retrieval – oh, so gentle Bacterial production and biological DMS turnover are strongly inhibited under surface irradiance conditions Leucine incorporation (nM h-1) 0.1 0.2 0.4 0.5 Dark incubated sample 5 10 0.3 Full spectrum light at depth 15 20 Leucine incorporation is an index of bacterial protein production 0.0 0 Incubation depth (m) Incubation depth (m) 0.0 0 Biological DMS loss rate constant (d-1) 5 10 0.1 0.2 0.3 0.4 0.5 0.6 Dark incubated sample Full spectrum light at depth 15 20 In situ quartz tube deployment - April 23, 2000 Central Gulf of Mexico In permitting the ozone layer to be destroyed and the intensity of UV at the Earth's surface to increase, we are posing challenges of unknown but worrisome severity to the fabric of life on our planet. We are ignorant about the complex mutual dependencies of the beings on Earth ad what the sequential consequences will be if we wipe out some especially vulnerable microbes on which larger organisms depend. We are tugging at a planet wide tapestry and do not know whether one thread only will come out in our hands, or whether the whole tapestry will unravel before us. Carl Sagan, Billions and Billions, 1997 The quality of light is important! Shorter wavelengths have higher energy per photon. These photons can cause reactions that would not occur (or would occur at slower rates) with longer wavelength photons. This is why the UV-B part of the spectrum is important! UV-B drives many photochemical reactions UV-B also directly affects biological systems DNA absorbs UV-B directly, causing thymine-thymine dimers and other DNA damage. Harmful effects of UV are only significant if rate of damage exceeds rate of repair (see work of J. Cullen and co-workers). UV-A (320-400 nm) may also be harmful because there are more photons of this relatively high energy radiation Chlorofluorocarbon gases increased dramatically in the atmosphere but now appear to be leveling off. Many CFC’s are long lived in the atmosphere and are potent greenhouse gases CFC-11 is just one type CFC http://lifesci.ucsb.edu/~biolum/chem/ Great animation on light generation and fluorescence http://lifesci.ucsb.edu/~biolum/chem/ Important photoproducts in seawater Compounds which are photochemically produced Source H2O2 DOM+O2 CO (carbon monoxide) and CO2 DOM – humic substances COS (Carbonyl sulfide) Organic sulfur compounds Low molecular weight acids and DOM aldehydes (pyruvate, formaldehyde, acetaldehyde etc) Reduced metals DMSO Fe3+ and Mn4+ organic complexes, especially humic complexes DMS (dimethylsulfide) A 37% increase in DMS photolysis is predicted under ozone hole conditions Calculated spectral photolysis rate of dimethylsulfide in Antarctic seawater under ozone hole and non–ozone hole conditions. Ozone hole The Antarctic ozone hole - 1995 Dobson units Dobson units (a measure of atmos. Source: NOAA TOVS satellite ozone) column Gulf of Mexico Specific rate of light absorption of chromophoric DOM (Ka) plotted as a function of wavelength for estuarine and oceanic water. Note the differences in scales! Mobile Bay From Mopper and Kieber, 2000 CFC’s catalytically destroy stratospheric ozone Each molecule of CFC can destroy many molecules of ozone This destruction is especially severe at the poles such that ozone holes develop, letting in much more UV-B than normal. Ozone hole over a city for first time (from news story on MSNBC) Chile’s Punta Arenas is first urban area to fall under hole For two days last month the ozone hole, seen in purple, extended over Punta Arenas, Chile, located at the southwestern tip of South America. In general, ozone depletion is greater at higher latitudes. Thus, the decrease near Seattle will be greater than near Los Angeles, while Miami will see the smallest depletion of the three US cities. However, southern cities also have much higher incidence of UVB light; even with less depletion, the net increase in UVB can be greater. http://www.epa.gov/docs/ozone/science/marcomp.html High photolysis rates of DMS in surface layers may be offset by lower rates of biological consumption DMS photoxidation rate constant - 35S-DMS in quartz tubes incubated in situ - Station 4 DMS Total loss rate constant - and Bacterial production DMS loss rate constant (per day) 0.2 0.4 0.6 0.8 0.0 1.0 0 0 -5 -5 -10 Bacterial production scaled to dark DMS loss -15 -20 -25 light dark Leucine Leu dark Depth (m) Depth (m) 0.0 Fraction of DMS converted per day 0.2 0.4 0.6 0.8 -10 -15 -20 -25 light dark 1.0 Other Photoreactive inorganic species: Hydrogen peroxide H2O2 + UV-R •OH Adapted from: Smith et al. 1992. Ozone depletion: UV radiation and plankton biology in Antarctic waters. Science 255: 952 Electromagnetic spectrum Wavelength (λ) Gamma X- rays Ultraviolet UV-C UV-B Visible Infrared Radio waves UV-A Energy per photon All are forms of radiation Jargon: rays = photons = waves Components of Solar radiation UV-C 190-290 nm none reaches Earth surface UV-B 290-320 nm energetic photons, but few reach surface UV-A 320-400 nm less energy per photon, but more photons PAR 400-700 nm photosynthetically active radiation IR 700- >1000 nm Near Infrared (heat) (far IR is up to 300,000 nm)