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Marine pollution refers to the what? |
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Definition
direct or indirect introduction by humans of substances or energy into the marine environment
-(including estuaries), resulting in harm to living resources, hazards to human health, hindrances to marine activities including fishing, impairment of the quality of sea water and reduction of amenities. |
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Many pollutants/contaminants are naturally present name some? |
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Definition
metals hydrocarbons in oil halogenated chemicals |
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What dose makes a pollutant? |
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Examples of marine contamination |
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-Petroleum – Spills and chronic inputs -Nutrients & organic matter– eutrophication & hypoxia and changes in species composition (food webs); harmful algal blooms(HABs) -Trace metals and metalloids – esp. Hg -PCBs, and other halogenated (F, Cl, Br) chemicals (local hotspots and global contamination -Other modern use pesticides -Endocrine disrupting chemicals (EDCs) -Pharmaceuticals -Radioactive waste disposal -Chlorine&Disinfection by-products |
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Examples of marine pollution |
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Definition
-Plastics, trash, and floatable materials -Siltation – run-off, erosion, prop-wash, dredging -Organic enrichment of sediments – affects species and toxicity -Pathogens -Thermal pollution (cooling waters, climate change?) -Invasive species introduction -Noise -Acidification -Wetland destruction for development -Structures? Jetties/walls/islands….concerns even about windmills |
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milli=10^-3 micro=10^-6 nano=10^-9 pico=10^-12 *metals femto=10^-15 *metals atto=10^-18 *metals zeta=10^-21 *metals |
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need light
prefer darkness |
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the pH is going down in the ocean.... why? |
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Because there is more metal in the ocean |
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Where does the particle intake of the atmosphere/ocean come from? |
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-River -Soil erosion -vegetation -volconic activity -Man-made input -sediment |
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What happens in the Particle cycle? |
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Primary Prodction-> Biologcal cycle-> Turbulent Mixing-> Physical Advection Diffusion-> Biologcal cycle-> Particle Flux-> Biologcal cycle |
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How much algea passes 1,000 meters? |
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Definition
1%, most of it doesnt get past 1,000 |
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-The # of e- -By density -Transport |
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-Lewis acids (e- acceptors)of small, size & low polarizable -oxygen seeking O>N>S F->Cl->Br->I-
Transport routes.. Atmophilic metal (B,borderline) Mass trasport to the sea is greater through amtosphere then via river or streams |
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-Lewis acids of large size & high polarizable -Sulfur/nitrogen seeking S>N>O I->Br->Cl->F-
Transport routes.. Lithophilic Metals (A, borderline) Mass trasport is primarily via river or streams |
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looking for O2 carboxylate alcohol phosphate |
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-Mining -Iron&steel production -Industrial appication -Non-Ferrous metal prodution -Combustion of coal, oil, wood -Fertilizer |
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Concentration Factors Increase Inversely with what? |
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Definition
-Dissolved organic concentration -Competing ion concentration -Particulate load |
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Why phytoplankton are important? |
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Definition
-Phytoplankton lie at the base of most marine food webs, are known to concentrate some metals appreciably out of seawater, and can serve to introduce them into marine food webs -Phytoplankton can be sensitive to some toxic metals -Planktonic debris can influence the sinking and oceanic residence times of metals |
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Dry wt. Concentration Factor |
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Definition
DCF (=Kd) = moles Me / g particle ------------------------ moles Me / ml dissolved |
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-Proportional to ambient concentrations -Big difference between metals -Smaller differences between species |
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Ethylenediamine tetra-acetic acid -common of chelation of water |
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Metal concentration in sediments vs TOC (Total Organic Carbon) |
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Stongly complexed by DOC (dissolved organic carbon) |
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*Hg *Cu *Zn *Ag *Cd The extent of bio accumulation |
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the uptake of substances into or across tissues |
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Colloidally associated metals in seawater: |
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Definition
Al, Am, Ce, Pb, Po, Sn, Th |
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Insignificant association with colloids in seawater: |
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Intermediate association with colloids: |
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-oil spill -coral reproduction -growth ratedecrease -cyanide stun fish -coral mining -Blast fishing -Dredging -Nutrient Enrichment |
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Assimilation efficiency in copepods is a... |
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metal contcentration in tissuesof the preditor is higher then metalcontcentration then prey |
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The act or process of voiding or discharging undigested food as faeces.
-Sticking -liquid waste -excretion (fecal pellets) |
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Diet is more important than water (esspeally for fish) |
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Definition
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Metals bound to colloidal particles do not typically penetrate into algal cytoplasm, and consequently do not get assimilated by herbivores which ingest these cells. These metals get packaged into fecal pellets which sink rapidly. These metals do not build up appreciably in marine food chains and are not likely to be consequential as micronutrients or as toxicants in marine organisms. |
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Metals which display little association with colloidal particles bind directly to algal cells and have a greater chance of penetrating into the cytoplasm of these cells (either by diffusion or through enzymatic activity). Some of these metals that are used as micronutrients, can become toxic to marine organisms, and are assimilated by herbivores in proportion to their penetration into the cytoplasm of single cells. These metals are released from dying cells or sinking biogenic debris at rates comparable to organic carbon and are generally recycled in surface waters through biological activity, consequently have longer oceanic residence times. |
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e- transport *Redox metal
-Any subsdance is bad if you use to much |
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alcohol dehydrogenase 2nd important |
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are organisms made up of cells that lack a cell nucleus or any membrane-encased organelles. |
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are organisms made up of cells that possess a membrane-bound nucleus (that holds genetic material) as well as membrane-bound organelles. |
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Advantages in using radiotracers in studying metal bioaccumulation in aquatic organisms |
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Definition
1.Rapid, accurate, and precise measurements of metals/metalloids using, for many elements of environmental concern, low environmentally realistic concentrations 2.When using gamma-emitting radiotracers, it is possible to make measurements (of several radionuclides) non-destructively 3.faster and generally cheaper |
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Problems associated with using radiotracers to study contaminant-biota interactions |
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Definition
1.toxicity problems 2.Care should be taken to assess chemical and physical speciation of added radioisotope to ensure that it is comparable to that of stable 3.radioisotopes can be rapidly exchanged between dissolved and particulate phases |
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Phytoplankton concentrate metals to varying extents, with relatively small differences between species. Uptake is generally passive and proportional to ambient metal concentrations. |
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Sinking pp aggregates can vertically transport metals to intermediate depths. Generally, metals which penetrate into algal cytoplasm are released at rates ≈ org. C from dying/decompressing cells. |
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Zooplankton “package” particle-reactive metals into rapidly sinking debris. They assimilate elements in proportion to cyto-plasmic distribution |
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Particle-reactive metals typically display short residence times & low AE’s in zp, they display scavenging-type profiles. |
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No biomagnification of metals up the food chain. Organisms with highest surface: volume have highest CFs. |
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-Shift in species composition -Total biomass/productivity do not necessarily change -In heavily polluted waters there is often a high biomass but reduced species diversity -“r” selected organisms often more pollutant-tolerant than “k” selected organisms |
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lethal concentration, concentration of metal that kills 50% of a population |
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effective or sublethal concentration, the concentration of metal that depresses growth rate by 50% in a population |
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Ionic forms generally toxic to marine life, some chelated form _______ ______. |
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Definition
harm less.
ex. Plankton-Interference with algal cell division rates, photosynthesis, and respiration Invertebrates-Larvae of oysters, shrimp, crabs, & lobsters up to 1000x Fish-Adults generally insensitive |
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Some mechanisms of microbial resistance to toxic metals |
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Definition
1. Energy-driven efflux pumps 2. Oxidation 3. Biosysnthesis of intracellular compounds to trap metal ions 4. Metal binding by cell surfaces 5. Precipitation of insoluble metal complexes 6. Biomethylation (e.g., Hg) and transport through cell membranes by diffusion-controlled processes. |
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make less of the element -makes its less toxic |
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make more of the other elements -makes its more toxic |
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There is no evidence to support food chain magnification of most metals (notable exception |
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Sinking planktonic detritus vertically transports metals in a predictable manner |
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Excessive richness of nutrients in a lake or other body of water, frequently due to runoff from the land, |
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Harmful Algal Blooms -gelatinous zooplankton -tinafores |
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-light limiting -less mixing -less O2 -stratifation -population |
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swim @ the bottom (will be affected more with Eutrophication |
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-stratifatired bay -salitity, Anoxic in the summer -light penetration decreased in the 80s |
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-Hypoxic in the gulf -the system has memory |
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-Hyper-Eutrophied *Forge River -Duck farms -Oxiadied Iron+Ulva *sea lecuttuce =Milky water -DO=noon(12pm)=photosystisis |
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Eelgrass with epiphyte growth |
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Epiphyte cover had a positive effect on seagrass growth in shallow water but had no effect on growth in deeper water. |
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3 types of sewage treatment |
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Primary treatment Secondary treatment Tertiary treatment |
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How many people don’t have access to an adequate supply of drinking water? |
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really settling sometimes with polymers... [screens] |
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biological treatment with acclimated bacteria |
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-Remove N and P nutrients. ***P removal by precipitation with lime or Al or Fe oxides -NH4+ removal by ammonia stripping. -Remove organics through filtration by activated carbon or membrane filtration |
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Passage through a gas many ion pairs (i.e., separate positive gaseous ions and electrons)
Straight line paths; generally, the range of an α particle varies as the sq. root of the atomic wt. and inversely as the density of the medium |
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Electrons or positrons
Number of ion pairs cm-2 of path (i.e, airspecific ionization)<<<α particles.
Βeta particles faster, travel further, easily deflected - - travel several m in air
Range inversely proportional to density of the medium |
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NOT charged particles & not deflected in electric or magnetic fieldsreleased by atoms in excited, high-energy state (as a result of release of α or β particle); excess energy above that in ground state emitted as a photon of r radiation
No direct production of ion pairs; the r-ray photon able to eject an electron with high energy which can behave like a β particle.
Greatest penetration |
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measures amount of energy lost in air by x-rays or gamma rays through ionization |
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Naval Testing 1960's __% radionuclides are from humans? |
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1% most of radioactivity is natural 30% of radioactive waste medical wastes |
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Disposal Methods: Isolation and Confinement |
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New packaging method is being considered to resist corrosion and thermal damage Sediments generally have a large sorptive capacity to prevent radioactive wastes from escaping into seawater above |
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reactor fire released 90 million Ci of Uranium, Plutonium, 90Strontium, 131Iodine, 137Cesium. Distributed over much of Europe, most concentrated in what is now the Ukraine and Belarus
Belarus’s children suffer: 100 fold increase in thyroid cancer 43% increase in disorders of the nervous system 43% increase in blood circulation illnesses 28% increase in disorders of the digestive system 62% increase in disorders of the bone, muscle, and connective tissues 1 in 3 children are ill |
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have different sizes (this affects e.g., hydrophobicity or ability to bind with enzyme or receptor binding sites), polarity, reactivity, acid/base character, charge, etc |
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Synthetic forms now a large part of insecticide market and some can be stable Permethrin, Resmethrin, Fenvalerate and many others… |
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The organohalogens are important environmental contaminants due to persistence, bioaccumulation, and potential for long range transport |
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Why the interest in organic contaminants in marine systems? |
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Humans are exposed daily to numerous chemicals that can harm their health and seafood is sometimes a major source of exposure – as opposed to metals where there are fewer cases (Hg, e.g.) where seafood a major source Aquatic toxicology As tracers of water movement (e.g., freons), of sediment history reconstructions (e.g, DDT residues), or of contaminant or organic matter sources in water (e.g., solvent and pharmaceuticals) or sediments (e.g, fecal sterols; nonbiodegradable fabric softeners) |
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Organophosphate pesticides |
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organophosphorous ester insecticides on the market. |
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Persistent Organic Pollutants -over 90 countries promised to reduce or eliminate the production, use, and release of 12 key POPs – the “dirty dozen”. |
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Persistent Bioaccumulative and Toxic |
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endocrine disrupting compounds |
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polycyclic aromatic hydrocarbons |
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Polybrominated diphenyl ethers (are used as flame retardants) |
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Name a few of the "dirty dozen" |
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1. Aldrin 2.Chordane 3. DDT 4.Dieldrin 5.Endrin 6.Heptachlor 7. Heptachlorbenzene 8. Mirex 9. Toxaphene 10.PCBs 11. Dioxins 12. Furans |
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Polychlorinated Hydrocarbons |
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Definition
All the dirty dozen are polychlorinated hydrocarbons They are stable and do not readily degrade to less toxic forms Persist in the environment for a long time and can bioaccumulate through the food chains Insoluble in water; sediments are important reservoirs; transported worldwide in atmosphere; soluble in fats Polychlorinated hydrocarbons of particular historical environmental concern are DDT, dioxins and PCBs |
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organic wastewater contaminants (OWCs) |
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at high concentration in sludges and biosolids and sometimes in organisms– they can persist in muddy sediments; most not transported in air; many probably not threats |
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endocrine disruptors/wastewater contaminants/ Pharmaceuticals |
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Feminization of male fish (e.g. testis-ova induction) Alteration of serum steroid levels Modulation of receptors, and proteins Potential impacts on both human?? and environmental health |
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the pressure of a vapor exerted from a liquid or solid compound. Units are in atmospheres. This term indicates how “volatile” a compound is and is important in understanding whether it will evaporate. |
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Van der waals interactions: |
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short range attraction related to polarizability and for this course remember highly dependent on the molecular size of the compound |
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Factors Influencing Solubility of a Given Compound in Water |
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Size Polarity H-bonding Temperature Salinity pH (if it is ionizable – acid/base) Dissolved organic matter (DOM) affects measured concentrations passing filters |
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An increase in concentration of contaminant moving up the food web..sometimes one compares lipid normalized concentrations to compare organisms as more lipid rich organisms can bioaccumate higher levels under equilibrium conditions |
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Organochlorine hydrocarbon Stable – half-life years Persistent Semi-volatile Low aqueous solubility Lipophillic – partitions into organisms Bioaccumulates Broad spectrum – toxic to wide variety of animals Low cost |
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At its introduction it seemed to be an ideal insecticide: Cheap to produce Was apparently non-toxic to humans and other mammals Did not breakdown easily → continued to kill insects for a long time after application However, water contaminated with DDT had a devastating effect on fish-eating birds By the 1960s, populations of bald eagles, peregrine falcons and brown pelicans had plummeted Insects became increasingly resistant to DDT and larger amounts had to be applied to have the desired effects (unfortunately resistance to some DDT replacements also a problem) |
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Production stopped in 1977 in USA Disposal of PCB-containing products now strictly regulated → dramatic decrease in PCB contamination of fish found in some cases but not others Different species have somewhat different enzymes that can oxidize some PCB congeners – hydroxylated PCBs prevalent in blood of some organisms (e.g., polar bears) and binds strongly to proteins – important thyroid hormone disrupting compounds in polar bears Because they are highly stable they persist in the environment Produced in Russia and many developing countries till more recent times? |
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Where is POPs&PCBs most previliant? |
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the Arctic because Atmospheric circulation, River inflow,Ocean currents |
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Indoor and outdoor air House and office dust Rivers, lakes and sediments Sewage sludge Biota (terrestrial and marine mammals, fish, humans), including common foods Remote Arctic regions (i.e., long-range transport) |
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- Perfluorooctane sulfonate |
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Surfactants are among the most produced chemicals in the world (>10 millions of tons per year) due to their wide range of applications… |
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- Cleaners and detergents - Personal care products - Pharmaceuticals products - Other uses: Pesticide adjuvants Wetting agents Paint additives … |
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