Illegal drugs and therapeutic opiates in the wastewaters of the city of Zagreb – estimation of collective

consumption and comparison with epidemiological data

Senka Terzic, Ivan Senta, Marijan AhelDivision for Marine and Environmental Research, Rudjer Boskovic Institute,

Bijenicka 54, 10000 Zagreb, Croatia, e-mail:terzic@irb.hr

Wastewater analyses

Exposure levels of drugs in the environment

Current usage patterns in a given local community

Wastewater- a source of different types of contaminantsIllegal drugs – widespread wastewater contaminants

Sampling strategy

Forensic aspects of wastewater analyses

-implemented by Zuccato et al. (2005, 2008)

Assumptions:•All drug residues found in wastewater derive from the human excretion•Negligible transformation of DTRs in the sewer system•No sewage water loss in the sewer system

Amount of the drug or its metabolite determined in wastewater corresponds with its collective consumption in a given local community

WWTP details and sampling strategy

February – September 200939 RW samples39 SE samples

Central wastewater treatment plant of the city of Zagreb

24-h composite samples2 * 9 consecutive days (spring and summer)9 weeks, Sun i Tue (19.04.-16.06.2009.)

WWTP details:Full mechanical and biological treatmentConventional activated sludge treatmentServing 650 000 inhabitants (≈ 83 % of the total population number)

SPE extraction OASIS HLB

LC-MS-MS (ESI +, MRM)

Mass loads (g/day) = daily excreted amounts (g/day)

Drug consumption (g/dan)

DTR concentration (g/m3)

24 h composite WW samples

WW flow rates (m3/day)

Zuccato et al. 2005, 2008

DTR excretion rates

Molar ratios

Filtration; GF/C

List of analysed DTRs

13,4-methylendioxymethamphetamine211-nor-9-carboxy-Δ9-tetrahydrocannabinol32-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP)

DTR Drug Drug category

Morphine Heroin, ( morphine, codeine)

lllegal drug, opioid, (opioid therapeutic drugs)

6-Acetyl morphine Heroin lllegal drug, opioid

Cocaine Cocaine lllegal drug, psychostimulans

Benzoylecgonine Cocaine lllegal drug, psychostimulans

MDMA1 Ecstasy lllegal drug, psychostimulans

Amphetamine Amphetamine lllegal drug, psychostimulans

THC-COOH2 Cannabis lllegal drug, cannabinoid

Methadone Methadone Therapeutic opioid drug, drug-addict treatment

EDDP3 Methadone Therapeutic opioid drug, drug-addict treatment

Codeine Codeine Therapeutic opioid drug, analgesic

Occurence of selected DTRs in RW wastewater

Removal efficiency in WWTP

Average daily mass loads of selected DTRs = daily excretion

Variability of mass loads of stimulant drugs on weekdays and on weekends

2.7 fold average increase of MDMA mass load on weekends

1.7 fold average increase of BE mass load on weekends

Daily variations of stimulating drugs

Representative daily mass loads of selected DTRs

DTR Mass load weekend (g/day) Mass load weekday (g/day) Representative value

Xw SDw Xwd SDwd

Morphine 76 11 74 16 75

6-Acetylmorphine 2.5 1.0 3.3 1.1 3,1

Amphetamine 2.5 2.3 1.7 1.5 1,9

MDMA 3.4 2.0 0.8 0.5 1,6

Benzoylecgonine 60 9.1 41 8.1 46

Cocaine 17 5.9 14 6.0 15

THC-COOH 16 3.9 16 6.4 16

Methadone 12 3.4 12 3.6 12

EDDP 29 2.9 30 3.7 30

Codeine 58 5.9 64 7.3 62

2/7 Xw + 5/7 Xwd

DrugDrug target residue (DTR)

Percentage of drug dose excreted as DTR (%)

Correction factor Dose (mg)

Cocaine Benzoylecgonine 45a 2.3 100Heroin Morphine 42a 3.1 30Cannabis THC-COOH 0.6a 152 125Amphetamine Amphetamine 30a 3.3 50Ecstasy (MDMA) MDMA 65a 1.5 100Methadone1 EDDP 3-25b 3.6 -Codeine Codeine 70c 1.4 -

Drug target residues, average excretion rates and average drug doses used to back calculate drug consumption

- not used for back calculationaadopted from Zuccato et al. 2008bBaselt 2004; a maximal value of 25 % was used to back calculate methadone consumption in this study. caverage excretion of codeine as a parent compound and/or conjugate (Osselton et al., 2003).

Back-calculation of drug consumption

Illicit drug consumption in the city of Zagreb based on wastewater analyses

Consumption units Heroin Cocaine Ecstasy Amphetamine Cannabiskg/year2 75 47 1 3 1051mg/day/1000 inh. 262 166 3.6 9.7 3690mg/day/1000 inh. 15-64 y1 408 235 5.1 14 5214

Cannabis >> heroin > cocaine >> amphetamines

Consumption profiles in Croatia and other countries

*

* mg/day/1000 inh 15-64 y

Comparison with the literature

2500

*mg/day/1000 inh. 15-64 y

*

*

Comparison with the epidemiological data

Number of treated addicts in the city of Zagreb (Katalinić et al. 2009)

Daily consumption (dose/day/1000 st. 15-64 y) estimated in this study

2 doses/day/consumer

≈ 3700 heroin consumers

1612 treated heroin addicts

≈ 40 % involved in treatment

HEROIN

0.5 doses/day/consumer

≈ 3300 cocaine consumers

86 treated cocaine addicts

< 3 % involved in treatment

COCAINE

Conclusion

Monitoring of selected drugs in representative WW samples could provide:• instantaneous information on the current consumption patterns•a reliable approach for the assessment of possible changes in drug abuse trends

An attractive complementary tool for the assessment of socio-epidemiological risks associated with drug abuse

Further evaluation and development of the applied methodology is needed

Thank you for the attention!

City of ZagrebInstitute of Public Health “Dr. Andrija Štampar”Staff of the central treatment water plant of the city of Zagreb” , to Marin Ganjto, especiallyNenad Muhin

Acknowledgment