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

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. 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. 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. 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. 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. 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. 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. 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. 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. Movement and fate of pollutants in the aquatic environment

11. Pollution of lakes

12. Pollution of ground water

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. Major water pollutants and their sources

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. 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. 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. 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. 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. Monitoring chemical pollutants in water

21. Laboratory analysis of chemicals in
water

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. Analytical instrumentation
chromatograph
various mass spectrometers

24. Gas chromatography/mass spectrometry system

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. Mass spectra of organic
compounds – this gives a
definitive identification of
a chemical pollutant by
looking a key ions (m/e)

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. 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 - http://en.wikipedia.org/wiki/DDT
Highly persistent in the environment and
can be bio-accumulated and bio-magnified by
different species in the food chain.

29. Pharmaceuticals and personal
care products (PPCPs) –
an emerging threat!?

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. 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. Also personal care and other
household products

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

35. Most of population at some time are polluters!

36. 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

37. Pharmaceuticals in Fish
National Geographic, April 2010.

38. 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

39. 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.

40. 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

41. 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

42. 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

43. 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

44. 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

46. 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)

47. 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

48. 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

49. 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.

50. Emerging problems with disposal
of electronic goods – E-waste

51. E-waste receipt and recovery of metallic components in Accra,
Ghana

52. 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.

54. What can you do?
Ways to help reduce water pollution

55. 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

56. 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.

57. 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

58. Any questions?