Drugs of abuse in wastewater and suspended particulate matter--further developments in sewage epidemiology.

This manuscript reports, for the first time, a monitoring study analysing wastewater and associated suspended particulate matter (SPM) to determine the concentration of drugs of abuse and metabolites in wastewater influent. The monitoring of SPM is crucial for target analytes because, depending on their physico-chemical properties, they may partition to particulates; thus, analysis of wastewater only will result in under-reporting of the concentration of target analytes in the sample. A daily one week monitoring study was carried out at a WWTP serving one of the largest cities in the Czech Republic; representing the first comprehensive application of the sewage epidemiology approach in the Czech Republic. In total, 60 analytes were targeted in the monitoring programme including stimulants, opioid and morphine derivatives, benzodiazepines, antidepressants, dissociative anaesthetics, drug precursors and their metabolites. Analysis of SPM determined that significant proportions of some compounds were present on the solids. For example, 21.0-49.8% of the total concentration of EDDP (2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine) in the sample was determined on SPM and 11.2-19.6% of methadone. The highest proportion on SPM was determined for fluoxetine in the range 68.1-79.6%, norfluoxetine 46.6-61.9% and amitriptyline 21.8-51.2%. In contrast, some compounds presented very little partitioning to SPM. Less than 5% was determined partitioned to SPM over the week period for analytes including cocaine, benzoylecgonine, cocaethylene, amphetamine, methamphetamine, MDMA (3,4-methylenedioxymethamphetamine), codeine, dihydrocodeine, tramadol, nortramadol, oxazepam and ephedrine. Determined concentrations in wastewater influent were subsequently utilised in the sewage epidemiology approach to estimate drug consumption, in the community from which the wastewater was derived. This back-calculation was updated for the first time to include the concentration of analytes present on SPM. The consumption of methamphetamine and MDMA was determined to be especially high in the studied community in relation to other European countries, while cocaine and methadone consumption was relatively low. This manuscript shows that in order to apply the sewage epidemiology approach, SPM analysis is required for some compounds; whereas for others the partitioning is small and one may regard this as negligible.

Application of different extraction methods for the determination of selected pesticide residues in sediments.

Using several extraction methods including the QuEChERS approach, samples of both model and natural sediments were prepared. For the isolation of the target group of pesticides, two variants of two complementary extractions had to be used. Resulting extracts were analysed with LC/MS/MS. Selected methods furnishing the best results were validated in the terms of linearity and repeatability. Their limits of detection ranged from 0.1 to 2 ng/g, their limits of quantification from 1 to 6 ng/g and their recovery percentage varied between 46 % and 102 %.

Systematic method for the incorporation of the {(eta(6)-arene)Fe} fragment into carborane cages via [(eta(6)-arene)Fe]2+ dications. A series of [3-(eta(6)-arene)-closo-3,1,2-FeC2B9H11] complexes. Reliable synthesis of polymethylated [(eta(6)-arene)2Fe]2+ cations.

Developed was a systematic method for the incorporation of the {(eta(6)-arene)Fe} fragment into a carborane cage. Reactions between [(eta(6)-arene)(2)Fe](PF(6))(2) salts and Tl(2)[nido-7,8-C(2)B(9)H(11)] in refluxing (CH(2))(2)Cl(2) generated a series of [3-(eta(6)-arene)-closo-3,1,2-FeC(2)B(9)H(11)] neutral complexes with variable types of polymethylated arene ligands in the structure. The structures of durene and hexamethylbenzene complexes were established by X-ray diffraction analyses. The work also shows that the original high-temperature method for the preparation of the [(eta(6)-arene)(2)Fe](2+) dications fails for mesitylene and durene compounds, which was overcome by a reliable room-temperature modification.

Boron(8) substituted nitrilium and ammonium derivatives, versatile cobalt bis(1,2-dicarbollide) building blocks for synthetic purposes.

The reaction of the cobalt bis(dicarbollide)(1-)() ion in the presence of t-butylbromide, acting as a potent Lewis acid activator, leads to the clean substitution of by the N-atom of acetonitrile (or benzonitrile), thus resulting in the smooth formation of [(8-RCN)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))-3,3'-Co(iii)](0) (R = CH(3) or C(6)H(5)) ( and ). These compounds can serve as versatile precursors for the generation of a variety of other synthetically useful functional groups. The nitrogen atom of the nitrile C[triple bond, length as m-dash]N- bond in and is prone to the facile addition of nucleophiles. Thus, alkaline hydrolysis of and in aqueous alcohols furnishes high yields of the corresponding B(8)-N-alkylamides [(8-RC(O)=NH)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))-3,3'-Co(iii)](-), where R = CH(3) or C(6)H(5) ( and ). The reactions with butyl and diethyl amine result in the high-yield formation of 8-alkylamidine derivatives [(8-(3)R(2)RNH-(1)RC[double bond, length as m-dash]N)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))-3,3'-Co(iii)](0), where (1)R = CH(3), (2)R = H, (3)R = C(4)H(9), (), (1)R = C(6)H(5), (2)R = (3)R = C(2)H(5) () or (1)R = C(6)H(5), (2)R = (3)R = C(2)H(5) (). Hydrazinolysis of provides a high yield of the zwitterionic [(8-H(3)N)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))-3,3'-Co(iii)](0) (), whereas reduction of the nitrile group in and using BH(3).SMe(2) affords the respective alkylammonium derivatives [(8-RH(2)N)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))-3,3'-Co(iii)](0), where R = -C(2)H(5) () or -CH(2)C(6)H(5) () in moderate yields. Compound can also be prepared by alkylation of along with dibenzylderivative (). A further example of alkylation is the ring cleavage of the 3-hydroxypropanesulfonic acid gamma-sultone producing a compound with alkyl ammonium sulfonic acid substitution [(8-O(3)SC(3)H(6)NH(2))-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))-3,3'-Co(iii)](-) () All new compounds were characterized by multinuclear NMR spectroscopy and mass spectrometry and the structures of compounds , , and were established by X-ray crystallography.