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Prof Graham Mills - The Fate of Pharmaceutical Residues in the Aquatic Environment


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Professor Graham Mills presented his talk "The Fate of Pharmaceutical Residues in the Aquatic Environment"

A full background of what contaminates water, from Pharmacology and Agriculture. People passing medicines they have taken or disposing of them by throwing them down the toilet are causing major changes to fish and other water dwelling creatures.

- October 2014 - Cafe Scientifique Isle of Wight

Published in: Health & Medicine
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Prof Graham Mills - The Fate of Pharmaceutical Residues in the Aquatic Environment

  1. 1. Water, water everywhere but is it fit to drink? Graham Mills Faculty of Science University of Portsmouth UK Café Scientifique Isle of Wight Branch, Shanklin 13th October 2014
  2. 2. Water, water everywhere but not a drop to drink The Rime of the Ancient Mariner English poet – Samuel Taylor Coleridge written in 1797-98
  3. 3. Outline of talk • Water, water cycle • Water pollution • Types of pollution • Chemical pollutants • Analysis of pollutants • Examples – hydrocarbons and pesticides – pharmaceuticals and personal care products • Recent emerging issues – electronic goods • Some solutions • Any questions?
  4. 4. Water – some facts • 75% of earths surface water. • Of all the Earth's water, about 97 % is salt water. • Only 1% of the Earth's water is available for drinking water. • Since 1940 the world’s water use has quadrupled whilst the world’s population has only doubled. • 1.8 billion people still lack access to fresh water supply and 2.5 billion people need improved sanitation. • 90% of the 30,000 deaths that occur every week from unsafe water and unhygienic living conditions are in children under five years old. • Half of the world’s hospital beds are occupied by patients suffering water borne diseases. • Water-related diseases kill one child every 15 seconds.
  5. 5. Distribution of water on Earth Nearly 97% of the world’s water is salty or otherwise undrinkable. Another 2% is locked in ice caps and glaciers. That leaves just 1% for all of humanity’s needs — all its agricultural, residential, manufacturing, community, and personal needs.
  6. 6. Water in the UK • Due to the lack of large-scale man made and natural water storage facilities in the UK water is scarce in many areas, however, the demand for water is growing at a steady rate of ~ 1% per year. • Each day the average person in the UK uses roughly 150 litres of water. • Industry and commerce in the UK consume 1,300 million cubic metres of water every year. • In the UK more than 150,000 litres of water are used to manufacture a new car, including tyres. • But 5 litres of petrol can potentially contaminate 4 million litres of clean water!
  7. 7. Earth’s overall water cycle Ocean Evaporation Evapo-transpiration runoff Water Supply Discharge treated water Salt Water Intrusion Soil moisture Aquifer Infiltration Recharge Evaporation Extraction Precipitation Precipitation Evaporation/ET Surface Water Groundwater Soil moisture Infiltration (Art) Extraction Return flow Treated water Aquifer intrusion Soil moisture
  8. 8. Water Pollution • Can be defined as any chemical, biological, thermal or physical change in water quality that harms living organisms (flora and fauna) or makes water unsuitable for desired uses. • Huge number of possible effects to consider in different environments. • Different forms of pollution: - non-point sources - scattered and diffuse and cannot be traced to any single site of discharge. - point sources - discharge pollutants at specific locations.
  9. 9. Point and non-point sources of water pollution NON-POINT SOURCES Urban streets Suburban development Wastewater treatment plant Rural homes Cropland Animal feedlot Factory POINT SOURCES
  10. 10. Movement and fate of pollutants in the aquatic environment
  11. 11. Pollution of lakes
  12. 12. Pollution of ground water
  13. 13. Industry Nitrogen oxides from autos and smokestacks, toxic chemicals, and heavy metals in effluents flow into bays and estuaries. Cities Toxic metals and oil from streets and parking lots pollute waters; sewage adds nitrogen and phosphorus. Urban sprawl Bacteria and viruses from sewers and septic tanks contaminate shellfish beds and close beaches; runoff of fertilizer from lawns adds nitrogen and phosphorus. Construction sites Sediments are washed into waterways, choking fish and plants, clouding waters, and blocking sunlight. Farms Runoff of pesticides, manure, and fertilizers adds toxins and excess nitrogen and phosphorus. Red tides Excess nitrogen causes explosive growth of toxic microscopic algae, poisoning fish and marine mammals. Toxic sediments Chemicals and toxic metals contaminate shellfish beds, kill spawning fish, and accumulate in the tissues of bottom feeders. Oxygen-depleted zone Sedimentation and algae overgrowth reduce sunlight, kill beneficial sea grasses, use up oxygen, and degrade habitat. Healthy zone Clear, oxygen-rich waters promote growth of plankton and sea grasses, and support fish. Closed shellfish beds Closed beach Oxygen-depleted zone
  14. 14. Major water pollutants and their sources
  15. 15. Pollution of water by chemicals • Over 10,000 chemicals enter the aquatic environment from different sources. • Quantities inputted vary significantly: few kg to thousands of tonnes. • Each chemical has a different impact in terms of toxicity and potential harm - accumulation and persistence and fate. • Chemicals usually sub-divided into heavy metal, inorganic and organic pollutants. • Inputs of only some of these chemicals are regulated by legislation in Europe (and elsewhere). • Most chemicals are still unregulated.
  16. 16. Main water quality legislation in Europe • The Water Framework Directive (WFD) is designed to improve the way water is managed in Europe. • It came into force on December 2000. Member States must aim to reach good chemical and ecological status in inland and coastal waters by 2015 subject to certain limited exceptions. It is designed to: - Enhance the status and prevent further deterioration of aquatic ecosystems and associated wetlands which depend on the aquatic ecosystems. - Promote the sustainable use of water. - Reduce pollution of water, especially by ‘priority’ and ‘priority hazardous’ chemical substances. - Ensure progressive reduction of ground water pollution.
  17. 17. Chemical pollutants in the WFD Priority substances 33 substances or groups of substances are on the list (2008/105/EC) for which environmental quality standards were set in originally 2008, including selected existing manufacturing chemicals, plant protection products, biocides and metals. Examples include: • polyaromatic hydrocarbons (PAH) – fuels and combustion by-products • polybrominated biphenylethers (PBDE) - flame retardants in products • high usage pesticides for crop protection • wide range of other high volume, historically used industrial chemicals • few metals such as cadmium, lead, mercury and nickel 12 new compounds of concern were added to the list in 2013 (Directive 2013/39/EU). 3 further compounds added to – so called Watch List 2013 (pharmaceutical products - Diclofenac, 17 alpha-ethinylestradiol and 17 beta-estradiol). The United States (EPA) has more priority chemicals on its lists.
  18. 18. WFD environmental quality standards (EQSs) • Environmental (water) Quality Standards tell us the quantity of a chemical pollutant that can safely be present in the water body without causing harm to the ecology and ideally that presents no significant risk to human health. • Within the WFD, EQSs are used for assessing the state of the water environment through classification, and are used as the fundamental measurements in the water quality monitoring programmes. • EQS represent a legally acceptable level of risk to the aquatic environment. • EQS are defined as both the maximum and average permissible concentration of a potentially hazardous chemical in an water sample (usually in terms of μg/L or ng/L concentrations). • National environment agencies in Europe have a legal obligation to ensure that the statutory EQSs are being met. • Standards are revised (normally downwards) in the light of new scientific data (see Directive 2013/39/EU).
  19. 19. Analysis of chemicals in water • Key to the protection of the aquatic environment and for the enforcement of legislation is the accurate and precise analysis of the different pollutants present in water. • This is large academic, commercial (water suppliers) and governmental (DEFRA, Environment Agency, SEPA, NRW) undertaking in the UK with many £ millions spent each year. • Most of the work is performed in dedicated analytical laboratories that operate under strict quality control procedures. • Most of the analysis is from bottle samples of water – typically 1-10 litres. • But a number of other monitoring methods are used.
  20. 20. Monitoring chemical pollutants in water
  21. 21. Laboratory analysis of chemicals in water
  22. 22. Analytical techniques • All analytical procedures use sophisticated instrumental techniques. • High cost: £50,000-£300,000 per instrument. • Organic pollutants: - Gas chromatography-mass spectrometry - Liquid chromatography-mass spectrometry • Inorganic pollutants: - Atomic absorption - Inductively coupled-mass spectrometry
  23. 23. Analytical instrumentation chromatograph various mass spectrometers
  24. 24. Gas chromatography/mass spectrometry system
  25. 25. Typical gas chromatogram showing the separation of c. 30 different pollutants – the area of each peak gives the relative concentrations in the sample after calibration.
  26. 26. Mass spectra of organic compounds – this gives a definitive identification of a chemical pollutant by looking a key ions (m/e)
  27. 27. Classical example of organic pollution of water – run off of DDT DDT was used in agriculture. In addition, it was used during the 1950-1960s to control various types of diseases, such as typhus and malaria. DDT has not been banned because in all regions an outright ban would have greater negative consequences than continuing to use it. DDT = Dichlorodiphenyltrichloroethane
  28. 28. Effects of DDT in the environment Egg shell thinning of specific bird’s eggs Dichlorodiphenyltrichloroethane or DDT, is a synthetic pesticide. It was largely used to control common agricultural pests. see - Highly persistent in the environment and can be bio-accumulated and bio-magnified by different species in the food chain.
  29. 29. Pharmaceuticals and personal care products (PPCPs) – an emerging threat!?
  30. 30. Pharmaceuticals – Why look for them? Environmental risks due to pharmaceuticals are now an important issue for environmental regulators. Driven by widespread detection of pharmaceuticals in environmental samples. Exposure of pharmaceuticals to aquatic life most likely from discharges from sewage treatment plants. Exposure (chronic) therefore at continuous low concentrations.
  31. 31. Emerging environmental threat – pharmaceuticals and antibiotics Anti-inflammatories Beta-blockers Contraceptives Anti-epileptics Anti-depressants Anti-biotics Anti-diabetics Lipid regulators Cytostatic agents Diuretics Muscle relaxants Others ……. X-ray contrast media Pharmaceuticals – diverse range of chemical products
  32. 32. Also personal care and other household products
  33. 33. Erythromycin (Anti-biotic) pKa = 8.8 logKow = 3.06 Omeprazole (Proton pump inhibitor) pKa = 4.0 & 8.8 logKow = 3.4 Atenolol (Beta-blocker) pKa = 9.3 logKow = 0.16 Salbutamol (Bronchodilator) pKa = 9.3 & 10.3 Trimethoprim (Anti-biotic) pKa = 7.3 logKow = 0.91 Fluoxetine (Anti-depressant) pKa = 8.7 logKow = 4.65 Carbamazepine (Anticonvulsant) logKow = 2.45 Diclofenac (NSAID and analgesic) pKa = 4.15 logKow = 4.51 Indomethacin (NSAID) pKa = 4.5 logKow = 4.27 Ketoprofen (NSAID) pKa = 4.5 logKow = 3.00 Propranolol (Beta-blocker) pKa = 9.5 logKow = 3.48 Sulfamethoxazole (Anti-biotic) pKa = 5.7 & 1.18 logKow = 0.48 Often described as POLAR compounds
  34. 34. Most of population at some time are polluters!
  35. 35. Concentrations of PPCPs found in the aquatic environment  Ever present environmental pollutants Waste Influent 1-10 μg/L Effluent low μg/L high ng/L Surface water 1 ng/L-1 μg/L Soil mg/kg Drinking water Ground water 0.1 ng/L low ng/L
  36. 36. Pharmaceuticals in Fish National Geographic, April 2010.
  37. 37. Environmental concerns of PPCPs • Little is known on their long-term impacts on aquatic and terrestrial ecology and human health • Chronic exposure (continual) to low concentrations • Inducing anti-biotic resistance and food chain issues • Newer cytostatic drugs – DNA and cell replication damage • Information needed on subtle effects, e.g. growth, fertility, behaviour - due to long-term low level exposures • Exposure of organisms to a cocktail of pollutants (effects of synergism?) or even antagonism? • Becoming a concern in Europe and USA and elsewhere • Public perception and education in use and disposal of PPCPs
  38. 38. Example of decline of gyps spp. vultures in Pakistan & India – possible link with drug - Diclofenac  Beginning in the early 1990s, vultures (especially white-backed vultures such as Gyps bengalensis) experienced dramatic population declines (as great as 95%).  Various hypothesized causes have ranged from pathogens to pesticides. The causative agent(s) result in acute kidney failure leading to death of the breeding population.  Prof. Oaks (Washington State University) presented evidence that deaths are strongly linked with diclofenac poisoning (“Diclofenac Residues as the Cause of Vulture Population Decline in Pakistan,” Nature, 28 January 2004).  Diclofenac, although primarily a human NSAID, is used in veterinary medicine in certain countries. In India, Diclofenac is used for treating cattle, whose carcasses are a major food source for Gyps.  Diclofenac seems to be selectively toxic to Gyps spp. versus other carrion-eating raptors.  In 2005 India phased-out the veterinary use of Diclofenac.
  39. 39. Anti-depressants: •They are many types in use: • selective-serotonin re-uptake inhibitors (SSRIs) • selective norepinethrine/serotonin reuptake inhibitors (SNRIs) • Serotonin antagonist and reuptake inhibitors (SARI) • Taken by 1 in 10 people in the US • Prescribed equally to the contraceptive pill • Found in rivers up to 1 μg/L (1,000ng/L), although on average concentrations are ~ 10-20 ng/L
  40. 40. Effects at 10 ng/L Olympic sized swimming pool 2,500,000 L = 25,000,000 ng = 25000 μg = 25 mg = 0.025 g = 4.2 g = 18,312 grains 109 grains of sugar
  41. 41. Significant effects on colour change and memory processing at 10 and 100 ng/L Fluoxetine in water Di Poi et al (2014). Cryptic and biochemical responses of young cuttlefish Sepia officinalis exposed to environmentally relevant concentrations of fluoxetine, Aquatic Toxicology, 151, 36-45 Di Poi et al (2013). Effects of perinatal exposure to waterborne fluoxetine on memory processing in the cuttlefish Sepia officinalis Aquatic Toxicology, 132–133, 84–91
  42. 42. Endocrine disrupting chemicals (EDCs) • Naturally occurring compounds or man-made chemicals that may interfere with the production or activity of hormones of the endocrine system. • EDCs are found in many products (pharmaceuticals, plastic bottles, flame retardants, …). • Some have been of historical concern for several decades. Some of the hormones linked to the endocrine system
  43. 43. How do EDCs work? Endocrine disruptors can influence the endocrine system and alter hormonal functions by: • partial or total mimicking naturally occurring hormones in the body • binding to a receptor within a cell → blocking the endogenous hormone from binding • interfering or blocking Mechanism of how EDCs work
  44. 44. WWTP – What to be aware off! • Metabolic conjugates (e.g. glucuronides, sulphates) of drugs can be back cleaved in the environment  actually increase concentration in WWTP final effluent • Formation of degradation products that are more toxic than the parent compound (e.g. chlorination  Paracetamol N-acetyl-p-benzoquinoneimine)
  45. 45. PPCPs – Advanced removal mechanisms at waste water treatment plants Ozonation  High potential for the removal of many PPCP  Effective for endocrine disruptors  Exception: iodinated contrast media Membrane filtration Other advanced oxidation processes  Processes aiming the formation of OH.  O3/H2O2, UV/H2O2, Fenton’s reagent  React unselectively  Nano-filtration, reverse osmosis (retention by molecular sieving) Expensive to install (retrofit) and operate these advanced systems
  46. 46. Main removal strategies of PPCPs in drinking water plants Elimination of micro-pollutants A) Removal processes: • Physical barrier  Membranes  Reverse osmosis • Physical retention  GAC, PAC B) Transformation processes: • Chemical oxidation  Ozone or chlorine  OH radicals • Photo-transformation • Advanced oxidation processes
  47. 47. Sewage epidemiology  Emerging field of recent environmental interest.  This concerns the determination of the exposure of a population to a chemical (e.g. prescription and non-prescription drugs) by analysis of parent compound or specific metabolites in waste-water influent.  By deploying specific samplers (e.g. passive samplers or auto-analysers) over extended time periods in the influent of a waste water treatment plant can give good estimates of drug usage within a given catchment population.  Epidemiological information obtained from such monitoring campaigns can help inform debates on drug policy, drug enforcement and on public health interventions.  Recent studies include analysis of waste water from hospitals, a prison and a sports complex.
  48. 48. Emerging problems with disposal of electronic goods – E-waste
  49. 49. E-waste receipt and recovery of metallic components in Accra, Ghana
  50. 50. Exposure routes, fate and behaviour of E-waste in the environment including contamination of food chains C. Frazzoli et al. Environmental Impact Assessment Review 30 (2010) 388–399.
  51. 51. What can you do? Ways to help reduce water pollution
  52. 52. Solutions: Industry • Reduce consumption • Recycle • Life cycle analysis – Modification of process to reduce consumption – New metrics are needed besides money • Public perception and expectations are driving many changes • Financial cost forces change
  53. 53. Solutions: Agriculture • Improved irrigation practices • Organic farming • Farming where it makes sense • Protect watersheds – BMPs – Control runoff Recycled water - used for years to irrigate vineyards at California wineries, and this use is growing.
  54. 54. Now is the time for innovation! • Water purification – Reverse osmosis – Forward osmosis – Ceramic pots – Solar desalination • Reduced water use • Water recycling • Watershed management – Protection, preservation • Infrastructure improvements
  55. 55. Any questions?