Risk-based prioritization of pharmaceuticals in the natural environment in Iraq

Numerous studies have demonstrated the occurrence of pharmaceuticals in the natural environment, raising concerns about their impact on non-target organisms or human health. One region where little is known about the exposure and effects of pharmaceuticals in the environment is Iraq. Due to the high number of pharmaceuticals used by the public health sector in Iraq (hospitals and care centres) and distributed over the counter, there is a need for a systematic approach for identifying substances that should be monitored in the environment in Iraq and assessed in terms of environmental risk. In this study, a risk-based prioritization approach was applied to 99 of the most dispensed pharmaceuticals in three Iraqi cities, Baghdad, Mosul and Basrah. Initially, information on the amounts of pharmaceuticals used in Iraq was obtained. The top used medicines were found to be paracetamol, amoxicillin and metformin with total annual consumption exceeding 1000 tonnes per year. Predicted environmental concentrations (PECs) and predicted no-effect concentrations (PNECs), derived from ecotoxicological end-points and effects related to the therapeutic mode of action, were then used to rank the pharmaceuticals in terms of risks to different environmental compartments. Active pharmaceutical ingredients used as antibiotics, antidepressants and analgesics were identified as the highest priority in surface water, sediment and the terrestrial environment. Antibiotics were also prioritized according to their susceptibility to kill or inhibit the growth of bacteria or to accelerate the evolution and dissemination of antibiotic-resistant genes in water. Future work will focus on understanding the occurrence, fate and effects of some of highly prioritized substances in the environment

Re-evaluation of the conformational structure of sulfadiazine species using NMR and ab initio DFT studies and its implication on sorption and degradation

In the environment, the sorption and the degradation of organic pollutants are of increasing interest. The investigation of the chemical structures provides a basis for the development of a suitable binding model approach and for the mechanistic understanding of the chemical fate processes. The aim of this study was the identification of different species of the antibiotic compound sulfadiazine (SDZ) using (1)H and (13)C NMR experiments and ab initio density functional theory (DFT) calculations. In the neutral, aprotic solvent dimethylsulfoxide-d(6) (DMSO-d(6)), a new sulfadiazine structure containing an O-H-N hydrogen bond was identified. In the protic solvent water-d(2) and in dependence on pH and the position of the amidogen hydrogen atom nine possible SDZ conformations were analyzed and five structures were identified. Good conformity between theory and calculation of (1)H NMR was observed. Unfortunately, (13)C NMR is not sensitive enough for comparison and differentiation. In order to verify the identified structures, additional NBO/NLMO (natural localized molecular orbital) analyses were conducted (calculation of net atomic charges, bond polarity, atomic valence, and electron delocalization). Finally, conformation optimizations were performed in order to investigate the stability of the SDZ species. We showed that SDZ contains no S=O double bond, but that it has two S-O single bonds. Surprisingly, negative charges were observed at the pyrimidine nitrogen atom. With these results, the known structure of SDZ was revised. Studies of the geometrical structure and the torsion angles showed that SDZ is very flexible and can be easily fitted to the sorbent. These observations would explain the strong sorbance and hence the rapid formation of non-extractable residues in the environment because SDZ acts as a strong ligand. These results show that that the sulfonamide hydrogen is important for the biological activity but the pyrimidine nitrogen and the sulfonamide oxygen is responsible for the sorbance in environment

Transport of pharmaceuticals in columns of a wastewater-irrigated Mexican clay soil

The irrigation of agricultural land with wastewater is increasingly practiced in many parts of the world as a consequence of growing populations and urbanization The risks emerging from pharmaceuticals that are contained in wastewater for soils and groundwater have hardly been investigated We studied leaching and effects of naproxen. ibuprofen, bezafibrate, diclofenac, gemfibrocil. clarithromycin. trimethoprim, clindamycin, erythromycin, and metoprolol in a soil column experiment simulating an irrigation event with 8 6 cm of wastewater containing 20 mu g L-1 or 2000 mu g L-1 of each compound or of erythromycin alone The leached fraction of applied pharmaceuticals ranged from 0 1 +/- 0 1% (clarithromycin, 2000 mu g L-1) to 130 +/- 41 % (naproxen, 20 mu g L-1) and tended to increase with decreasing K-d or K-oc. Naproxen transport was similar to that of the tracer chloride Ibuprofen was also hardly retarded (R = 1 20 +/- 0 18). but showed a higher degradation rate of 0 02 +/- 0 004 h(-1) (2000 mu g L-1) than naproxen The transport of a pulse of 2000 mu g L-1 of bezafibrate could be described with a retardation factor of 1 5 and a degradation rate of 0.033 h(-1) The application of erythromycin alone or of a cocktail of all pharmaceuticals significantly Increased soil CO2 emissions by 50% 1 d after the application Mere is a considerable risk that pharmaceuticals are leached to groundwater during wastewater irrigatio

Bestimmung von Kofaktoren im marinen Sediment

In respect to a sieving study of sediments in three different sediment locations (Wadden Sea (A), river Elbe-Aestuar (B), Baltic Sea (C)) a determination of selected organic compounds were carried out to study the influence of the sieving process on the variance of cofactors and analytical results. The organic pollutants PCB, Organochlorpesticides (OCP) and PAH were investigated in three fine sediment fractions <2 mm, > and < 63 #mu#m of the locations by accredited and standardised methods. At the same time the cofactor Organic Carbon (TOC) as well as Total Carbon (TC) and Total Nitrogen (TN) were determined in the fine sediment fractions. The endocrine disruptor Bisphenol A could be detected in the sediment locations B and C. The comparison of TOC, TC and TN average values by t-test showed significant differences between the fine fractions of location B and C. Because of low TOC values no signification was detectable in sediment A. The results show that the TOC values in fine sediments are affected by sieving. An enrichment of carbon was detected in the <63 #mu#m fraction in consideration of variance. A correlation between the cofactor TOC and the organic pollutant values could only be detected in the fine fractions of location B. The enrichment of pollutant values in the fine fractions was here analogue of TOC. For a comprehensive evaluation of the cofactor TOC no sufficient sieving sample materials were available in this study for location A and C. So a final statement regarding TOC in fine sediment fractions as a cofactor was not possible. The results show that a determination of organic contaminants in the fine sediment fraction <63 #mu#m make sense because of their enrichment in fine fractions in respect to the TOC values. (orig.)SIGLEAvailable from TIB Hannover: RN 8908(2000,442) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekBundesministerium fuer Umwelt, Naturschutz und Reaktorsicherheit, Bonn (Germany)DEGerman

Untersuchung der Boeden im direkten Umfeld der UBA-Messnetz-Standorte in den neuen Laendern zur Vervollstaendigung des bundesweiten Umweltbeobachtungsnetzes im Hinblick auf ein integriertes und repraesentatives Monitoring

In the area of 11 FEA-monitoring-locations in Brandenburg (Doberlug-Kirchhain, Falkenberg, Neuglobsow, Schorfheide-Kienhorst), Mecklenburg-Vorpommern (Ueckermuende, Zingst), Saxony (Lehnmuehle, Lueckendorf, Melpitz) and Thuringia (Leinefelde, Schmuecke) there were sampled 103 soil profile pits with 488 horizons described in detail by the German soil taxonomy, 4"t"h edition (KA4) by the state geological services. The profile and horizon description followed the form of KA4 and was documented in an established Microsoft-Access 2000-Database. Beside the common physical and chemical soil data the inorganic and organic toxic pollutants were investigated. The particle-size distribution was calculated. Most of the soil profile pits were sandy soils (70%) or loam soils (10%). Some soils were defined as clay and silt soils or fens. For the evaluation of the inorganic soil parameters like C_t, pH value and CEC were summarized as horizon groups based on the field measurements. To compare the concentration levels of inorganic toxic pollutants with background data referred to the common land use were taken according to the legend-units of the map of soil reference materials (MPM 1000). To determine Quality Assurance parameters of inorganic pollutants several investigations were carried out by simultaneous measurements via KW/ICP-AES, RFA-(S) and -(P) of the same horizon. According to the background data there were higher concentrations of Pb, Cr and Zn in the sandy horizons. For PAK following concentration gradient of accumulation for land use was observed: field<forest (conifers)<grassland (swath)<grassland<forest (organic matter). DDT, #gamma#-HCH, DDT and PCBs were detected in several samples. In addition to endocrine disrupters (Bisphenol A, Nonylphenol and Phthalate) were determined. The PAK- and Phthalate-levels were in the same range. (orig.)Im Umfeld der 11 UBA-Luftmessnetzstationen in Brandenburg (Doberlug-Kirchhain, Falkenberg, Neuglobosow, Schorfheide-Kienhorst), Mecklenburg-Vorpommern (Ueckermuende, Zingst), Sachsen (Lehnmuehle, Lueckendorf, Melpitz) and Thueringen (Leinefelde, Schmuecke) wurden 103 Schuerfgruben mit 488 Horizonten entsprechend der Bodenkundlichen Kartieranleitung, 4. Auflage (KA4) durch die Geologischen Dienste der jeweiligen Bundeslaender aufgenommen und beprobt. Die profil- und horizontbezogene Dokumentation der Ergebnisse erfolgte nach dem Formblatt der KA4 und in einer dafuer entwickelten Datenbank mit Microsoft Access 2000. Im Labor wurden neben allgemeinen physikalischen und chemischen Parametern auch Gehalte an anorganischen und organischen Schadstoffen bestimmt. Bei den Untersuchungen zur Korngroessenzusammensetzung konnte die Mehrzahl der erfassten Schuerfgruben der Bodenartenhauptgruppe Sand (70%) zugeordnet werden. Weitere 10% waren Lehmboeden und der Rest entfiel auf Moorstandorte sowie Schluff- bzw. Tonboeden. Fuer die Auswertung der allgemeinen anorganischen Parameter C_t, pH-Wert und KAK_p_o_t wurden die im Gelaende angesprochenen Horizonte zu Horizontgruppen zusammengefasst. Fuer den Vergleich der gemessenen anorganischen Schadstoffgehalte mit Hintergrundwerten erfolgte die Zuordnung der Standorte zu den Legendeneinheiten der Karte der Bodenausgangsgesteine (BAG 1000). Durch den gleichzeitigen Einsatz der KW/ICP-AES und RFA-(S) und -(P) Verfahren bei der Bestimmung von anorganischen Schadstoffen durch die beteiligten Labore an Proben der selben Horizonte mit separater Probenvorbereitung konnten laborexterne Ueberpruefungen zur Richtigkeit der Pruefergebnisse durchgefuehrt werden. Allgemein wurden erhoehte Gehalte an Pb, Cr und Zn gefunden. Darueber hinaus bestehen auch Tendenzen zur Anreicherung von PAK in der Reihenfolge Acker<Forst, Nadelbaeume<Gruenland, Mahd<Gruenland<Forst, Streu. Ebenfalls nachzuweisen waren #gamma#-HCH, DDT und PCB im Boden. Zusaetzlich erfolgte die Bestimmung von endokrin wirksamen Stoffen (Bisphenol A, Nonylphenol und Phthalate). Dabei wurden zu den PAK vergleichbare Phthalatgehalte bestimmt. (orig.)SIGLEAvailable from TIB Hannover: RN 8908(2000,393) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekBundesministerium fuer Umwelt, Naturschutz und Reaktorsicherheit, Berlin (Germany)DEGerman