| Title | Simultaneous determination of human pharmaceuticals in water samples by SPE and HPLC with UV-fluorescence detection |
| Abstract | The production of pharmaceutical substances for human and veterinary use exceeds
thousands of tons per year worldwide and only in the EU about 3,000 drugs are currently in
use. Human pharmaceutical products can enter into the sewer system through the urine and
faeces discharged to wastewater treatment plants (WWTPs). Since conventional wastewater
treatment processes are not specifically designed to remove them, the effluents from
WWTPs can still contain remarkable amounts of pharmaceuticals and metabolites.
Consequently, drug occurrence in surface water and groundwater at trace levels (<1 g/L)
has been recently recognized.
Their presence in the aquatic environment can have adverse effects on biotic communities
with changes in morphological and metabolic or endocrine functions. The registration and
marketing of drugs are exempted from REACH regulation and, currently, a procedure to
establish their possible environmental impact is not required. However, because of their
ubiquitous presence in the environment, pharmaceuticals may be candidates for future
regulation regarding the water protection. A threshold value of 10 ng/L in surface water has
been recently suggested in Europe for some classes of drugs. This value has been largely
exceeded in several Italian rivers, e.g. concentrations ranging from 0.1 to 250 ng/L have
been found in the Po River.
Accurate and sensitive methods are therefore necessary for the detection of several
pharmaceuticals in wastewaters as well as in the aquatic ecosystems. HPLC-MS and
GC-MS have generally been used to determine pharmaceuticals in water samples. However
when analyzing highly contaminated samples, such as wastewater, a suppression of the
electrospray ionization is likely to occur. Moreover, these instruments are quite expensive
and, consequently, not widely distributed.
The purpose of our study is to present a procedure to determine selected drugs in water
samples by applying HPLC with simultaneous UV and fluorescence (FL) detection. The
method here developed is sufficiently sensitive and of simple application for routine
determination of nine pharmaceutical residues of different therapeutic classes (the
anti-epileptic carbamazepine; the lipo-regulators gemfibrozil, clofibric acid and fenofibrate;
the anti-inflammatories ibuprofen, naproxen, ketoprofen and diclofenac) and three steroid
hormones (17beta-estradiol, 17alpha-etinilestradiol, estrone) in both wastewater and surface
water. The method involved sample pre-concentration and clean-up by SPE using polymeric
Strata-X extraction cartridges. Final analysis of the selected pharmaceutical compounds was
carried out by HPLC-UV-FL (abs=230 nm for UV detector; exc=230nm, emiss=302 nm for
FL detector) using a C18 analytical column and a gradient elution with acetonitrile:water
(pH=3.6). The chromatographic run was 40 min. Average recoveries were in the range
83-97% with relative standard deviations below 13%. The detection limits were in the range
5-40 ng/L for both wastewater and surface water. The optimized method has been
successfully applied for the detection of the selected drugs in some influent-effluents from
municipal WWTPs close to the city of Rome (Italy) and from contaminated sites along the
urban stretch of the Tiber River. |
| Source | XIV Hungarian-Italian Symposium on Spectrochemistry:Analytical Techniques and Preservation of Natural Resources, Sümeg, Hungary, 5-7 ottobre 2011 |
| Year | 2011 |
| Type | Contributo in atti di convegno |
| Authors | Patrolecco L., Ademollo N., Barra Caracciolo A., Capri S., Grenni P., Tolomei A. |
| Text | 89842 2011 Simultaneous determination of human pharmaceuticals in water samples by SPE and HPLC with UV fluorescence detection Patrolecco L., Ademollo N., Barra Caracciolo A., Capri S., Grenni P., Tolomei A. Istituto di Ricerca sulle Acque, Roma The production of pharmaceutical substances for human and veterinary use exceeds thousands of tons per year worldwide and only in the EU about 3,000 drugs are currently in use. Human pharmaceutical products can enter into the sewer system through the urine and faeces discharged to wastewater treatment plants WWTPs . Since conventional wastewater treatment processes are not specifically designed to remove them, the effluents from WWTPs can still contain remarkable amounts of pharmaceuticals and metabolites. Consequently, drug occurrence in surface water and groundwater at trace levels <1 g/L has been recently recognized. Their presence in the aquatic environment can have adverse effects on biotic communities with changes in morphological and metabolic or endocrine functions. The registration and marketing of drugs are exempted from REACH regulation and, currently, a procedure to establish their possible environmental impact is not required. However, because of their ubiquitous presence in the environment, pharmaceuticals may be candidates for future regulation regarding the water protection. A threshold value of 10 ng/L in surface water has been recently suggested in Europe for some classes of drugs. This value has been largely exceeded in several Italian rivers, e.g. concentrations ranging from 0.1 to 250 ng/L have been found in the Po River. Accurate and sensitive methods are therefore necessary for the detection of several pharmaceuticals in wastewaters as well as in the aquatic ecosystems. HPLC MS and GC MS have generally been used to determine pharmaceuticals in water samples. However when analyzing highly contaminated samples, such as wastewater, a suppression of the electrospray ionization is likely to occur. Moreover, these instruments are quite expensive and, consequently, not widely distributed. The purpose of our study is to present a procedure to determine selected drugs in water samples by applying HPLC with simultaneous UV and fluorescence FL detection. The method here developed is sufficiently sensitive and of simple application for routine determination of nine pharmaceutical residues of different therapeutic classes the anti epileptic carbamazepine; the lipo regulators gemfibrozil, clofibric acid and fenofibrate; the anti inflammatories ibuprofen, naproxen, ketoprofen and diclofenac and three steroid hormones 17beta estradiol, 17alpha etinilestradiol, estrone in both wastewater and surface water. The method involved sample pre concentration and clean up by SPE using polymeric Strata X extraction cartridges. Final analysis of the selected pharmaceutical compounds was carried out by HPLC UV FL abs=230 nm for UV detector; exc=230nm, emiss=302 nm for FL detector using a C18 analytical column and a gradient elution with acetonitrile water pH=3.6 . The chromatographic run was 40 min. Average recoveries were in the range 83 97% with relative standard deviations below 13%. The detection limits were in the range 5 40 ng/L for both wastewater and surface water. The optimized method has been successfully applied for the detection of the selected drugs in some influent effluents from municipal WWTPs close to the city of Rome Italy and from contaminated sites along the urban stretch of the Tiber River. 978 963 9970 22 9 XIV Hungarian Italian Symposium on Spectrochemistry Analytical Techniques and Preservation of Natural Resources Sumeg, Hungary 5 7 ottobre 2011 Internazionale Contributo Atti Convegno Internazionale Abstract Book Convegno Internazionale AttiUngheria_2011_Patrolecco.pdf Contributo in atti di convegno nicoletta.ademollo ADEMOLLO NICOLETTA luisa.patrolecco PATROLECCO LUISA anna.barracaracciolo BARRA CARACCIOLO ANNA paola.grenni GRENNI PAOLA silvio.capri CAPRI SILVIO TA.P04.005.011 Vulnerabilita degli ecosistemi delle acque sotterranee e attenuazione naturale degli inquinanti nel suolo e nel sottosuolo |
