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Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea Vladimir Nikiforov Institution of Russian Academy of Sciences Saint- Petersburg Scientific-Research Centre for Ecological Safety RAS (SRCES RAS)

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Page 1: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Pilot activity to identify sources and flow

patterns of pharmaceuticals in St Petersburg

to the Baltic Sea

Vladimir Nikiforov

Institution of Russian Academy of Sciences Saint-Petersburg Scientific-Research Centre for Ecological

Safety RAS (SRCES RAS)

SRCES RAS

Sources of legacy pollutants

Little household waste

Sources of emerging pollutants

Little Industrial waste

Project in brief

bull Study on WWTP samples (ca 100 samples) bull Sewage water effluent sludge bull Seasonal dynamics (temperature light) bull Weekly dynamics bull Circadian dynamics (light) bull Surface water Neva Gulf of Finland bull Load assessment treatment assessment

consumption correlation

Environmental ndash social science Narcotics in sewage Milano

Name Surname

472014 6

Ettore Zuccato Chiara Chiabrando Sara Castiglioni Renzo Bagnati and Roberto Fanelli Estimating Community Drug Abuse by Wastewater Analysis

Environ Health Perspect 2008 August 116(8) 1027ndash1032 doi 101289ehp11022

Diclofenac

bull Painkiller bull Anti-inflammatory (NSAID) bull Pills injections gelsointments etc

17α-ethynylestradiol (EE2)

bull Semi-synthetic steroidal estrogen bull Oral contraceptive bull Estrogen

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 2: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

SRCES RAS

Sources of legacy pollutants

Little household waste

Sources of emerging pollutants

Little Industrial waste

Project in brief

bull Study on WWTP samples (ca 100 samples) bull Sewage water effluent sludge bull Seasonal dynamics (temperature light) bull Weekly dynamics bull Circadian dynamics (light) bull Surface water Neva Gulf of Finland bull Load assessment treatment assessment

consumption correlation

Environmental ndash social science Narcotics in sewage Milano

Name Surname

472014 6

Ettore Zuccato Chiara Chiabrando Sara Castiglioni Renzo Bagnati and Roberto Fanelli Estimating Community Drug Abuse by Wastewater Analysis

Environ Health Perspect 2008 August 116(8) 1027ndash1032 doi 101289ehp11022

Diclofenac

bull Painkiller bull Anti-inflammatory (NSAID) bull Pills injections gelsointments etc

17α-ethynylestradiol (EE2)

bull Semi-synthetic steroidal estrogen bull Oral contraceptive bull Estrogen

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 3: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Sources of legacy pollutants

Little household waste

Sources of emerging pollutants

Little Industrial waste

Project in brief

bull Study on WWTP samples (ca 100 samples) bull Sewage water effluent sludge bull Seasonal dynamics (temperature light) bull Weekly dynamics bull Circadian dynamics (light) bull Surface water Neva Gulf of Finland bull Load assessment treatment assessment

consumption correlation

Environmental ndash social science Narcotics in sewage Milano

Name Surname

472014 6

Ettore Zuccato Chiara Chiabrando Sara Castiglioni Renzo Bagnati and Roberto Fanelli Estimating Community Drug Abuse by Wastewater Analysis

Environ Health Perspect 2008 August 116(8) 1027ndash1032 doi 101289ehp11022

Diclofenac

bull Painkiller bull Anti-inflammatory (NSAID) bull Pills injections gelsointments etc

17α-ethynylestradiol (EE2)

bull Semi-synthetic steroidal estrogen bull Oral contraceptive bull Estrogen

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 4: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Sources of emerging pollutants

Little Industrial waste

Project in brief

bull Study on WWTP samples (ca 100 samples) bull Sewage water effluent sludge bull Seasonal dynamics (temperature light) bull Weekly dynamics bull Circadian dynamics (light) bull Surface water Neva Gulf of Finland bull Load assessment treatment assessment

consumption correlation

Environmental ndash social science Narcotics in sewage Milano

Name Surname

472014 6

Ettore Zuccato Chiara Chiabrando Sara Castiglioni Renzo Bagnati and Roberto Fanelli Estimating Community Drug Abuse by Wastewater Analysis

Environ Health Perspect 2008 August 116(8) 1027ndash1032 doi 101289ehp11022

Diclofenac

bull Painkiller bull Anti-inflammatory (NSAID) bull Pills injections gelsointments etc

17α-ethynylestradiol (EE2)

bull Semi-synthetic steroidal estrogen bull Oral contraceptive bull Estrogen

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 5: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Project in brief

bull Study on WWTP samples (ca 100 samples) bull Sewage water effluent sludge bull Seasonal dynamics (temperature light) bull Weekly dynamics bull Circadian dynamics (light) bull Surface water Neva Gulf of Finland bull Load assessment treatment assessment

consumption correlation

Environmental ndash social science Narcotics in sewage Milano

Name Surname

472014 6

Ettore Zuccato Chiara Chiabrando Sara Castiglioni Renzo Bagnati and Roberto Fanelli Estimating Community Drug Abuse by Wastewater Analysis

Environ Health Perspect 2008 August 116(8) 1027ndash1032 doi 101289ehp11022

Diclofenac

bull Painkiller bull Anti-inflammatory (NSAID) bull Pills injections gelsointments etc

17α-ethynylestradiol (EE2)

bull Semi-synthetic steroidal estrogen bull Oral contraceptive bull Estrogen

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 6: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Environmental ndash social science Narcotics in sewage Milano

Name Surname

472014 6

Ettore Zuccato Chiara Chiabrando Sara Castiglioni Renzo Bagnati and Roberto Fanelli Estimating Community Drug Abuse by Wastewater Analysis

Environ Health Perspect 2008 August 116(8) 1027ndash1032 doi 101289ehp11022

Diclofenac

bull Painkiller bull Anti-inflammatory (NSAID) bull Pills injections gelsointments etc

17α-ethynylestradiol (EE2)

bull Semi-synthetic steroidal estrogen bull Oral contraceptive bull Estrogen

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 7: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Diclofenac

bull Painkiller bull Anti-inflammatory (NSAID) bull Pills injections gelsointments etc

17α-ethynylestradiol (EE2)

bull Semi-synthetic steroidal estrogen bull Oral contraceptive bull Estrogen

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 8: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

17α-ethynylestradiol (EE2)

bull Semi-synthetic steroidal estrogen bull Oral contraceptive bull Estrogen

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 9: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Analytical method ndash based on EPA 1694

bull Method 1694 Pharmaceuticals and Personal Care Products in Water Soil Sediment and Biosolids by HPLCMSMS Washington December 2007

bull ca 80 different pharmaceutical substances

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 10: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

LCMS Tandem mass-spectra of Diclofenac Standard solution

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 349 MA 82144975

616 701 884 089 230

00 05 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Time (min)

0

50

100

RT 351 MA 80813508

662 549 789 916 106 205

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400

mz

0

10000000

20000000

Inte

nsity

29602

29802

30002 21505 39128 25002 27801 23500 29362 16975 19818 13510 11733 14902 26601 37500 15896 18750 33294 33999 35596 31392 10296

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

mz

0

500000

Inte

nsity

29602 27801

25002 21505

16975 19761 25776 8783 6237 29846 29362 32806 16173 19054 8266 33874 32110 22316 12006 26895 24227 12703 20533 35004 10319 13705

MS1 SIM

MS2HCD 15

MS1 SIM

MS2 HCD 15

NH

OHO

ClCl

NH

ClClNH

Cl Cl

LCMS IT-TOF ESI(-)

-OH -CO -H+ -CO2

mz 29501 precursor

mz 2500196 Ion ndash product (-) mz 2500185 Ion ndash product (+)

mz 293994 Diclofenac

mz 30002 C13-Diclofenac

Ms2 CID E50 ColGas 75

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 11: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Ethynylestradiol

LTQ Orbitrap

bull Robust Accurate Mass ndash 5 ppm rms external calibration ndash 2 ppm rms internal calibration

bull High Resolution ndash 60000 at mz 400 with a scan

repetition rate of 1 Hz ndash Maximum Resolution gt100000

bull Mass Range ndash 50-2000 200-4000

bull Sub-fmol Sensitivity ( lt 03 pg ) bull MSMS and MSn

bull High Dynamic Range ndash gt2500 within mass spectrum

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 12: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Ethynylestradiol Ion introduction

including part-coated gold-plated octopole amp novel lens arrangement

Two-stage gridless reflectron

ESI or APCI

interfaces

Ion focusing optics including the

Q-Array

Differentially pumped quadrupole ion trap with pulsed argon introduction

Time of flight analyserOrthoganol source geometry with counter

gas flow

LC-MS IT-TOF

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 13: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Diclofenac Central WWTP 3 weeks

Vladimir Nikiforov

472014 13

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 14: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Diclofenac sales and consumption

Vladimir Nikiforov

472014 14

bull Official data not available bull Public statistics is a) inconsistent b) in rubles or in

ldquopackagesrdquo bull Diclofenac Ortofen Voltaren Diklak etc bull Ointment 20-100g 1-5 of substance ndash 15My bull Ampoules 100mg 5pack ndash 8My bull Pills 100mg 10-100pack ndash 13My bull Suppositories 100mg 5pack ndash 1My bull Russia ca 35My ca 20ty bull StPetersburg 700kgy = 850ngL in sewage

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 15: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Diclofenac in surface water

Vladimir Nikiforov

472014 15

bull Monastyr bay Ladoga Lake Valaam(2011) 16-60 ngL bull Olginskoe lake (2011) 82 ngL bull The Karpovka river (2012) 42 ngL bull The Malaya Nevka river (2012) 133 ngL bull Primorsk Gulf of Finland (2012) 121 ngL bull Lakhta Razliv (2012) 39 ngL bull Detected highest concentration in other countries

5500 ngL

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 16: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Metabolism of Diclofenac and suggested reverse transformation

Vladimir Nikiforov

472014 16

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 17: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac

Vladimir Nikiforov

472014 17

Aertal 60 tabs 100mg (6g = 5g of Diclofenac) 713 rub Aertal 15 ointment 60g (09g = 075g of Diclofenac) 249 rub Market volume unknown

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 18: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

1st Sampling Series Central WWTP 3 weeks

Objectives vs Results

Vladimir Nikiforov

472014 18

bull To get a large representative set of data on DCF in sewage water and WWTP effluent

bull To determine variation between different days and weeks (x5 x17)

bull To attempt to determine weekly trend bull To follow ldquotreatment vs removalrdquo bull To determine the average (362gd) maximum bull To determine extent of removal (ca 10)

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 19: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Diclofenac Conclusions 1st series

Vladimir Nikiforov

472014 19

bull Annual input of SPB = 280 kilo bull 40 of consumption ndash in sewage bull Purification on WWTP = 10 bull Total Diclofenac - Definition bull Analytical method needed

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 20: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Diclofenac 2nd series

Vladimir Nikiforov

472014 20

bull Parallel sampling on 3 major WWTPs bull Monday(in)-Tuesday(out) and Tuesday(in)-

Wednesday(out) processing time close to 24 hours

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 21: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

EE2 and Population of Saint-Petersburg ния 2010 года (тыс чел)

По результатам подведения итогов Всероссийской переписи населения 2010 года Росстат произвел ретроспективный пересчет численности населения за 2003ndash2010 годы (письмо Петростата от 24092012 г ОН-1404645)

2013 120 thousand migrants

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 22: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Population diagram ma)

Женщины (26907 тыс чел) Мужчины (21889 тыс чел) Возраст лет

Большой разрыв в продолжительности жизни мужчин и женщин приводит к существенной деформации структуры населения по полу Превышение численности женщин над численностью мужчин отмечается во всех возрастных группах старше 25 лет и достигает наибольших значений в старших возрастных группах

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 23: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Release of EE2 and natural estrogens

Vladimir Nikiforov

472014 23

bull Consumption of EE2 ndash 950 thousand packages (0665 mg each)

bull 73 thousand women (6 ) bull Annual consumption ndash 630g bull 13 excreted ndash 210gyear input bull ca 033 ngL in sewage bull ca 0004ngL in ldquoStPetersburg waterrdquo bull EQS = 0007ngL bull Ca 65 thousand newborns in SPb in

2013 bull Ca 50 thousand pregant women

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 24: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Excretion (Input) of hormones into sewage

Vladimir Nikiforov

472014 24

Experimental Estrone (E1) ndash 20-100 ngL

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 25: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Excretion (Input) of hormones into sewage

bull Ethynylestradiol (EE2) 125 of estrogeneicity bull Natural estrogens of pregnant women (E1 E2 E3)

ca 23 of estrogeneicity bull Input from other regions (Leningrad region

Novgorod region Karelia Vuoksa basin of Finland) bull Cattle farms chicken farms (20 million in L region)

25 180000 cows 200000 swine

E1 40-100 kgyear (SPb - 18) E2 70-300 kgyear (SPb ndash 24)

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 26: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Динамика суммарного коэффициента рождаемости в Санкт-Петербурге

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 27: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

ldquoHormonal forecastrdquo

Vladimir Nikiforov

472014 27

bull Human excretion of natural estrogens will increase by ca 10 in the next 5y

bull Consumptionexcretion of EE2 - bull Excretion of natural estrogens will

approach the value of 1990 bull Population growth Immigrants ndash

male bull Farming has to be taken into account

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 28: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Other pharmaceuticals detected in SPb wastewater

Drotaverin (Но-шпа)

Ketoprofen (Кетопрофен)

Trimethoprim (Триметоприм)

Bendazol (Дибазол)

Ciprofloxacin (Ципрофлоксацин)

Clarithromycin (Кларитромицин)

Enalapril (Эналаприл) Enalaprilat

(Эналаприлат)

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 29: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents

Infl Effl WWTP1 WWTP2 WWTP3mean mean mean mean meanugl ugl ugl ugl ugl

1 Caffeine lt001 021 lt001 2 Ciprofloxacin 06 006 006 003 00153 Diclofenac 042 035 015 018 0184 Ketoprofen 206 037 036 039 0445 Ranitidin 0006 001 0036 Trimethoprim 0023 001 0027 Clarithromycin 049 039 038 Azythromicine 049 049 0469 Carbamazepine 035 072 0012 002 00110 Эритромицин 0056 003 00211 Metmorphyne 0003 0007 00212 Enalapryl lt0001 lt0001 lt000113 Drotaverin 0008 0003 000514 Enalaprylat 0001 lt0001 00215 Paracetamol lt005 lt005 lt00516 Ibuprophene 161 065 27 149 3517 Triclicarbane 018 031 079

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 30: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Ibuprofen in Saint-Petersburg

bull 08 of the SPb market in 2013 (stable share) bull Market ndash 800 M USD bull Ibuprofen ndash 64 M USD = 200 M Rub bull 50 x 200 mg = 17 rub bull 500 million units 5 million population bull 100 tons of substance (the same in Finland) bull A cube 10m x 10m x 10mhellip

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 31: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Diclofenac vs Ibuprofen

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 32: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Pharmaceuticals ndash emerging pollutants cooperation required

bull Market regulators bull Pharmaceutical industry bull Medical data on excretion bull Metabolites ndash reversibility bull WWTPs ndash different stages of treatment bull Environmental half-life times (temperature) bull Analytical methods incl metabolites bull Public awareness ndash understanding of our

world

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention
Page 33: Pilot activity to identify sources and flow patterns of ... at work/Projects/BASE/BSD Hazardous... · to identify sources and flow patterns of pharmaceuticals in St Petersburg to

Thank you for your attention

Little Industrial waste

  • Pilot activity to identify sources and flow patterns of pharmaceuticals in St Petersburg to the Baltic Sea
  • SRCES RAS
  • Sources of legacy pollutants
  • Sources of emerging pollutants
  • Project in brief
  • Environmental ndash social scienceNarcotics in sewage Milano
  • Diclofenac
  • 17α-ethynylestradiol (EE2)
  • Analytical method ndashbased on EPA 1694
  • Slide Number 10
  • Ethynylestradiol
  • Ethynylestradiol
  • Diclofenac Central WWTP 3 weeks
  • Diclofenac sales and consumption
  • Diclofenac in surface water
  • Metabolism of Diclofenac and suggested reverse transformation
  • Aceclofenac (Aertal Asinac) ndash possible precursor of Diclofenac
  • 1st Sampling Series Central WWTP 3 weeksObjectives vs Results
  • Diclofenac Conclusions 1st series
  • Diclofenac 2nd series
  • Slide Number 21
  • Slide Number 22
  • Release of EE2 and natural estrogens
  • Excretion (Input) of hormones into sewage
  • Excretion (Input) of hormones into sewage
  • Динамика суммарного коэффициента рождаемости в Санкт-Петербурге
  • ldquoHormonal forecastrdquo
  • Other pharmaceuticals detected in SPb wastewater
  • Concentration of selected pharmaceuticals in the SPb and Helsinki WWTPs effluents
  • Ibuprofen in Saint-Petersburg
  • Diclofenac vs Ibuprofen
  • Pharmaceuticals ndash emerging pollutantscooperation required
  • Thank you for your attention