Considering the worldwide growing discharge of minor actinides and the current need for geological disposal facilities for radioactive waste, this work provides a contribution to the safety case concerning Np transport if it would be released from deep repository sites and moving from alkaline cement conditions (near-field) to more neutral environmental conditions (far-field). The reducing conditions in a nuclear waste repository render neptunium tetravalent, which is assumed to be immobile in aqueous environment due to the low solubility solution of Np(IV). For tetravalent actinide nuclides, the most significant transport should occur via colloidal particles. This work demonstrates the formation of intrinsic neptunium dioxide nanocrystals and amorphous Np(IV) silica colloids under environmentally relevant conditions. The dissociation of the initial soluble Np(IV) complex (i.e. [Np(IV)(CO3)5]6-) induces the intrinsic formation of nanocrystalline NpO2 in the solution phase. The resulting irregularly shaped nanocrystals with an average size of 4 nm exhibit a face-centered cubic (fcc), fluorite-type structure (space group ). The NCs tend to agglomerate under ambient conditions due to the weakly charged hydrodynamic surface at neutral pH (zetapotential ~0 mV). The formation of micron-sized agglomerates, composed of nanocrystals of 2-5 nm in size, and the subsequent precipitation cause immobilization of the major amount of Np(IV) in the Np carbonate system. Agglomeration of NpO2 nanocrystals in dependence on time was indicated by PCS and UV-vis absorption spectroscopy with the changes of baseline characteristics and absorption maximum at 742 nm. Hitherto, unknown polynuclear species as intermediate species of NpO2 nanocrystal formation were isolated from solution and observed by HR-TEM. These polynuclear Np species appear as dimers, trimers and hexanuclear compounds in analogy with those reported for other actinides. Intrinsic formation of NpO2 (fcc) nanocrystals under ambient environmental conditions is prevented by admixing silicic acid: amorphous Np(IV) silica colloids are formed when silicate is present in carbonate solution. Herein, the initial molar ratio of Si to Np in solution lead to the formation of Np(IV) silica particles of different composition and size where Si content determines the structure and stability of resulting colloids. Implications for different electronic structures of Np(IV) in dependence on Si content in the solid phase are given by the shift of the absorption maximum at 742 nm characteristic for Np(IV) colloids, silica excess of 5 times the magnitude of Si to Np reveal a redshift up to 6 nm in the colloidal UV-vis spectrum. Precipitation of Np(IV) particles in the ternary system results in a different coordination sphere of Np(IV) compared to the binary system, and the incorporation of Si into internal structure of Np(IV) silica colloids in coffinite-like structure is confirmed by EXAFS. TEM confirms different kinds of particle morphologies in dependence on the silica content. Silica-poor systems reveal porous particles in the micron-range which consist of irregular cross-linked hydrolyzed Np(IV) silica compartments with pores <15 nm. In contrast, long-term stabilized and silica-enriched systems are characterized by isolated particles with an average particle size of 45 nm. Agglomerates of such isolated Np(IV) silica particles appear as consolidated amorphous solids with a densely closed surface and exhibit no internal fractures. The latter mentioned morphology of Np(IV) silica particles might facilitate the migration behavior of Np(IV) in a stabilized colloidal form under environmental conditions. The silica-enriched particles with densely closed surface are long-term stabilized as colloidal dispersion (>1 year) due to repulsion effects caused by significant surface charge. Particles synthesized from Si/Np = 9/1 carry exclusively negative surface charge in nearly the whole pH range from pH 3 to pH 10 with zetapotential = (-) 5 to (-) 30 mV. The zeta potentials of all particle systems containing silica are significantly shifted to more negative values below pH 7 where the isoelectrical point shifts from pH = 8.0 to 2.6 effecting negative charge under ambient conditions which supports electrostatic stabilization of Np(IV) particles. Particle surface charge at the slipping plane, particle size and shape necessarily depend on the initial magnitude of Si content in solution during particle formation. Particular changes of the morphology and internal structure of different Np(IV) silica colloids by aging are indicated by TEM and XPS. The composition and the crystallinity state of the initially formed amorphous phases partially changed into well-ordered nanocrystalline units characterized with fcc structure. The presence of silicate under conditions expected in a nuclear waste repository significantly influences the solubility of Np(IV) and provoke the stabilization of waterborne Np(IV) up to concentrations of 10-3 M, exceeding Np´s solubility limit by a factor of up 10.000. Neptunium and silicate significantly interact with each other, and thereby changing their individual hydrolysis and polymerization behavior. Silicate prevents the intrinsic formation of NpO2 NCs in fcc-structure, and at the same time, Np(IV) prevents the polymerization of silicate. Both processes result in the formation of Np(IV) silica colloids which possibly influence the migration behavior and fate of Np in the waste repositories and surrounding environments. For tetravalent actinides in general, the most significant transport in the environment would occur by colloidal particles. Therefore, Np(IV) silica colloids could have a significant implication in the migration of Np, the important minor actinide in the waste repositories, via colloidal transport.

Benzotriazoles (BTs) such as 1H-benzotriazole (1H-BT), 5-methyl-1H-benzotriazole (5Me-BT) and 4-methyl-1H-benzotriazole (4Me-BT) have a wide range of industrial applications. BTs are present for example in dishwasher detergents, in automotive antifreeze formulations and aircraft de-icing/anti-icing fluids (ADAF) as corrosion inhibitors. BTs belong to the group of “emerging contaminants” that have got in recent years more and more in the focus of environmental scientists, policy makers and the general public. These compounds are ubiquitous and highly mobile in the aquatic environment. It has been already shown that BTs have negative effects on aquatic organisms. The objective of the present study was among others to monitor 1H-BT, 4Me-BT and 5Me-BT in river- and wastewater. River water samples were taken from five rivers in the Hengstbach/Schwarzbach catchment area, a medium-sized catchment area of about 400 km². River water grab samples were taken during six different sampling. The aim of this monitoring study was to get a seasonal catchment-wide overview on measured concentrations and mass loads of BTs. BTs concentrations were determined in 24-hours influent composite samples taken on different month from three wastewater influents in Germany. In addition, 2-hours composite influent samples collected during one day in April were analyzed to determine the daily periodic emissions of BTs mass flows. Moreover, ADAF used at German airports and three dishwasher detergent tablets commonly used in Germany were analyzed for the presence of BTs to study the distribution pattern of those compounds in different products. An analytical method based on SPE and GC-MS has been developed and optimized for the determination of the presence of the corrosion inhibitors 1H-BT, 4Me-BT and 5Me-BT in environmental samples.

Considering the worldwide growing discharge of minor actinides and the current need for geological disposal facilities for radioactive waste, this work provides a contribution to the safety case concerning Np transport if it would be released from deep repository sites and moving from alkaline cement conditions (near-field) to more neutral environmental conditions (far-field). The reducing conditions in a nuclear waste repository render neptunium tetravalent, which is assumed to be immobile in aqueous environment due to the low solubility solution of Np(IV). For tetravalent actinide nuclides, the most significant transport should occur via colloidal particles. This work demonstrates the formation of intrinsic neptunium dioxide nanocrystals and amorphous Np(IV) silica colloids under environmentally relevant conditions. The dissociation of the initial soluble Np(IV) complex (i.e. [Np(IV)(CO3)5]6-) induces the intrinsic formation of nanocrystalline NpO2 in the solution phase. The resulting irregularly shaped nanocrystals with an average size of 4 nm exhibit a face-centered cubic (fcc), fluorite-type structure (space group ). The NCs tend to agglomerate under ambient conditions due to the weakly charged hydrodynamic surface at neutral pH (zetapotential ~0 mV). The formation of micron-sized agglomerates, composed of nanocrystals of 2-5 nm in size, and the subsequent precipitation cause immobilization of the major amount of Np(IV) in the Np carbonate system. Agglomeration of NpO2 nanocrystals in dependence on time was indicated by PCS and UV-vis absorption spectroscopy with the changes of baseline characteristics and absorption maximum at 742 nm. Hitherto, unknown polynuclear species as intermediate species of NpO2 nanocrystal formation were isolated from solution and observed by HR-TEM. These polynuclear Np species appear as dimers, trimers and hexanuclear compounds in analogy with those reported for other actinides. Intrinsic formation of NpO2 (fcc) nanocrystals under ambient environmental conditions is prevented by admixing silicic acid: amorphous Np(IV) silica colloids are formed when silicate is present in carbonate solution. Herein, the initial molar ratio of Si to Np in solution lead to the formation of Np(IV) silica particles of different composition and size where Si content determines the structure and stability of resulting colloids. Implications for different electronic structures of Np(IV) in dependence on Si content in the solid phase are given by the shift of the absorption maximum at 742 nm characteristic for Np(IV) colloids, silica excess of 5 times the magnitude of Si to Np reveal a redshift up to 6 nm in the colloidal UV-vis spectrum. Precipitation of Np(IV) particles in the ternary system results in a different coordination sphere of Np(IV) compared to the binary system, and the incorporation of Si into internal structure of Np(IV) silica colloids in coffinite-like structure is confirmed by EXAFS. TEM confirms different kinds of particle morphologies in dependence on the silica content. Silica-poor systems reveal porous particles in the micron-range which consist of irregular cross-linked hydrolyzed Np(IV) silica compartments with pores <15 nm. In contrast, long-term stabilized and silica-enriched systems are characterized by isolated particles with an average particle size of 45 nm. Agglomerates of such isolated Np(IV) silica particles appear as consolidated amorphous solids with a densely closed surface and exhibit no internal fractures. The latter mentioned morphology of Np(IV) silica particles might facilitate the migration behavior of Np(IV) in a stabilized colloidal form under environmental conditions. The silica-enriched particles with densely closed surface are long-term stabilized as colloidal dispersion (>1 year) due to repulsion effects caused by significant surface charge. Particles synthesized from Si/Np = 9/1 carry exclusively negative surface charge in nearly the whole pH range from pH 3 to pH 10 with zetapotential = (-) 5 to (-) 30 mV. The zeta potentials of all particle systems containing silica are significantly shifted to more negative values below pH 7 where the isoelectrical point shifts from pH = 8.0 to 2.6 effecting negative charge under ambient conditions which supports electrostatic stabilization of Np(IV) particles. Particle surface charge at the slipping plane, particle size and shape necessarily depend on the initial magnitude of Si content in solution during particle formation. Particular changes of the morphology and internal structure of different Np(IV) silica colloids by aging are indicated by TEM and XPS. The composition and the crystallinity state of the initially formed amorphous phases partially changed into well-ordered nanocrystalline units characterized with fcc structure. The presence of silicate under conditions expected in a nuclear waste repository significantly influences the solubility of Np(IV) and provoke the stabilization of waterborne Np(IV) up to concentrations of 10-3 M, exceeding Np´s solubility limit by a factor of up 10.000. Neptunium and silicate significantly interact with each other, and thereby changing their individual hydrolysis and polymerization behavior. Silicate prevents the intrinsic formation of NpO2 NCs in fcc-structure, and at the same time, Np(IV) prevents the polymerization of silicate. Both processes result in the formation of Np(IV) silica colloids which possibly influence the migration behavior and fate of Np in the waste repositories and surrounding environments. For tetravalent actinides in general, the most significant transport in the environment would occur by colloidal particles. Therefore, Np(IV) silica colloids could have a significant implication in the migration of Np, the important minor actinide in the waste repositories, via colloidal transport.

No description available.

Iron and manganese are relevant constituents of the earth's crust and both show increasing mobility when reduced by free electrons. This reduction is known to be controlled by microbial dissimilation processes. Alternative sources of free electrons in nature are cloud-to-ground lightning events with thermal and galvanic effects. Where thermal effects of lightning events are well described, less is known about the impact of galvanic lightning effects on metal mobilization. Here we show that a significant mobilization of manganese occurs due to galvanic effects of both positive and negative lightning, where iron seems to be unaffected with manganese being abundant in oxic forms in soils/sediments. A mean of 0.025 mmol manganese (negative lightning) or 0.08 mmol manganese (positive lightning) mobilization may occur. We suggest that lightning possibly influences biogeochemical cycles of redox sensitive elements in continental parts of the tropics/subtropics on a regional/local scale.

Iron and manganese are relevant constituents of the earth's crust and both show increasing mobility when reduced by free electrons. This reduction is known to be controlled by microbial dissimilation processes. Alternative sources of free electrons in nature are cloud-to-ground lightning events with thermal and galvanic effects. Where thermal effects of lightning events are well described, less is known about the impact of galvanic lightning effects on metal mobilization. Here we show that a significant mobilization of manganese occurs due to galvanic effects of both positive and negative lightning, where iron seems to be unaffected with manganese being abundant in oxic forms in soils/sediments. A mean of 0.025 mmol manganese (negative lightning) or 0.08 mmol manganese (positive lightning) mobilization may occur. We suggest that lightning possibly influences biogeochemical cycles of redox sensitive elements in continental parts of the tropics/subtropics on a regional/local scale.

Die Europäische Wasserrahmenrichtlinie schuf einen rechtlichen Rahmen, der die Mitgliedsstaaten zum Schutz der Wasserressourcen verpflichtete. Das Ziel ist das Erreichen eines guten ökologischen und chemischen Zustandes der europäischen Gewässer. Ein besonderes Augenmerk fiel in jüngerer Zeit auf die Rolle von Arzneimitteln als unerwünschte Chemikalien in der Umwelt. Arzneimittelwirkstoffe und ihre Rückstände konnten in vielen europäischen Gewässern nachgewiesen werden. Über die Auswirkung einer chronischen Exposition von Wasserorganismen auf Arzneimittelwirkstoffen ist nur wenig bekannt. Das künstliche Östrogen 17a-Ethinylestradiol (EE2) sorgt für Kontroversen, da es zur Aufnahme in die Liste der prioritären Stoffe der Wasserrahmenrichtlinie vorgeschlagen wurde. Der dazugehörige vorgeschlagene Grenzwert für Oberflächengewässer beträgt 35 pg/L als Jahresdurchschnitts-Umweltqualitätsnorm (JD-UQN). Einerseits gibt es Zweifel, ob der Grenzwert eingehalten werden kann und andererseits ist die Analytik bisher nicht in der Lage, EE2-Konzentrationen in dieser Größenordnung verlässlich messen zu können. Da keine Messwerte zur Gewässerbelastung durch EE2 existieren, hatte meine Arbeit das Ziel, den Einfluss der Abflussvarianz auf die EE2-Konzentration im Wasser zu untersuchen und zu prüfen, ob die Einhaltung des Grenzwerts möglich ist. Der Eintrag und Verbleib von EE2 wurde mittels des räumlich expliziten Modellsystems GREAT-ER in den deutschen Einzugsgebieten Ruhr und Main modelliert. Die damit berechneten EE2-Frachten im Gewässer wurden benutzt, um an ausgewählten Messstellen eine Simulation der Variabilität der EE2-Konzentrationen zu ermöglichen. Dazu wurde die Abflussvariabilität an den Messstellen anhand von langjährigen Pegeldatenreihen geschätzt. Die Ergebnisse zeigen, dass insbesondere in den Hauptläufen der Flüsse mit deutlichen Überschreitungen der JD-UQN in den Monaten von Mai bis Oktober zu rechnen ist. Mittels Monte Carlo-Simulation wurde das Risiko quantifiziert, wie häufig die JD-UQN im Jahresmittel überschritten würde. Für die Messstellen im Hauptlauf des Mains und im Unterlauf der Ruhr wurde ermittelt, dass dort mit hoher Sicherheit die JD-UQN nicht eingehalten werden kann. Auch an Messstellen, die im Jahresmittel den Grenzwert nicht überschritten, konnten häufige Überschreitungen des Grenzwerts in den Sommermonaten beobachtet werden. Die Zeiträume waren dabei lang genug, um relevant für chronische Effekte auf Wasserorganismen zu sein. Die durch die Oberflächengewässerverordnung vorgegebene Überwachung der JD-UQN erscheint daher für EE2 nicht sinnvoll. In Deutschland werden große Mengen von jodhaltigen Röntgenkontrastmitteln (JRKM) verbraucht (rund 370 Tonnen in 2009), die unverändert und in gesamter Menge über das kommunale Abwasser in Oberflächengewässer gelangten. JRKM sind nach Stand der Forschung toxikologisch unbedenklich, stellen aber aufgrund der teilweise hohen Konzentrationen im Bereich von ug/L eine Gefahr für die Trinkwasserversorgung dar. Trotz der hohen Verbrauchsmenge war bisher wenig über Emissionsmuster und Verbrauch von JRKM bekannt. Ziel der Arbeit war es daher, Informationen über den Verbrauch in medizinischen Einrichtungen zu sammeln und ein geeignetes Modell zu identifizieren, mit dem der Eintrag von JRKM in die Umwelt modelliert werden kann. Zu diesem Zweck wurden Modellansätze aus der Literatur als auch ein selbstentwickelter Ansatz im Modellsystem GREAT-ER implementiert und in den Einzugsgebieten Main und Ruhr simuliert. Die Ergebnisse zeigen, dass die Anzahl der Computertomographen als Proxygrößen zur räumlichen Aufteilung von JRKM-Emissionen verwendet werden kann. Rund zwei Drittel der jährlichen in Deutschland verbrauchten JRKM entfallen dabei nach eigenen Abschätzungen auf Krankenhäuser. Außerdem wurde gezeigt, dass der Nachweis von JRKM mittels Stichprobenmessungen in Gewässern und Kläranlagen in vielen Fällen keine belastbaren Aussagen liefert, da der Eintrag von wenig genutzten JRKM stark ereignisgetriebenen ist. Darüber hinaus konnten regionale Unterschiede in den Verbrauchsmengen identifiziert werden, die vermutlich auf lokal vorherrschende Präferenzen für einzelne JRKM zurück zu führen sind.

Ein kompetitiver ELISA (Enzyme-linked Immunosorbent Assay) für den Nachweis von Carbamazepin (CBZ) mit einer Bestimmungsgrenze von ca. 30 ng/L wurde entwickelt und validiert. Dieser in Gewässern häufig auftretende anthropogene Marker wurde anschließend in einer Vielzahl an Proben aus Abwässern, Oberflächengewässern und Trinkwässern nachgewiesen. Der ELISA zeigte eine exzellente Präzision und erbrachte in allen Matrizes geringfügig höhere Analysenergebnisse als die Referenzmethode HPLC-MS/MS. Die beständige Überbestimmung der CBZ-Konzentration in Höhe von ca. 7 % konnte auf die Präsenz von Cetirizin und geringen Mengen des persistenten Metaboliten 10,11 Epoxy¬carbamazepin (EP-CBZ) zurückgeführt werden. Die Bindungseigenschaften des verwendeten Antikörpers wurden anhand der Kreuz¬reaktivi¬täten von 37 Substanzen eingehend untersucht. Nach Kopplung von Flüssig¬chromato¬graphie und ELISA konnte das strukturell nicht mit CBZ verwandte Anti¬histaminikum Cetirizin als Kreuzreaktand identifiziert werden. Der störende Einfluss dieses Kreuz¬reaktanden auf den CBZ-ELISA konnte nach einer Änderung des pH-Wertes im Proben¬puffer minimiert werden. Die pH-abhängige Selektivitätssteuerung ermöglichte überdies die Entwicklung eines Dual-Analyt-Immunoassays für die parallele Bestimmung von CBZ und Cetirizin. Darüber hinaus wurden die Metaboliten EP-CBZ, DiOH-CBZ, 2-OH-CBZ, 3-OH-CBZ und 10 OH-CBZ in Abwasser, Oberflächenwasser und Trinkwasser quantifiziert. DiOH-CBZ erwies sich als ähnlich persistent wie CBZ und wurde in besonders hohen Konzentrationen gefunden. Außerdem wurden mehrere weitere bislang nicht identifizierte Abbauprodukte von CBZ gefunden. Da weder Probenvorbereitung noch Probenanreicherung erforderlich sind, ist der Test schnell und kostengünstig durchführbar. Die für den Test nötigen Probenvolumen sind mit weniger als 1 mL sehr gering. Diese Eigenschaften erlauben ein Hochdurchsatzscreening und machen die Methode interessant für den Einsatz im Gewässermonitoring. / A competitive ELISA (enzyme-linked immunosorbent assay) for the quantitation of carbamazepine (CBZ) was developed and validated. A limit of quantitation (LOQ) of ca. 30 ng/L allowed for the quantitation of CBZ in many samples from wastewater, surface water and drinking water. The method was found to be excellently precise, but it displayed slightly higher results than obtained by the reference method liquid chromatography-tandem mass spectrometry (LC-MS/MS). The nearly constant overestimation of 7 % could be attributed to the presence of small amounts of cetirizine and the persistent metabolite 10,11 epoxy¬carbamazepine (EP-CBZ). The binding properties of the antibody were studied by determining the cross-reactivities of 37 compounds. Hyphenating liquid chromatography to ELISA led to the discovery of the cross-reactive antihistamine cetirizine that shares no obvious structural similarity with CBZ. The bias caused by cetirizine was eliminated by changing the pH value of the sample buffer. Moreover, the antibody’s pH-dependent selectivity enabled a dual-analyte immunoassay for the parallel determination of CBZ and cetirizine. Furthermore, the metabolites EP-CBZ, DiOH-CBZ, 2-OH-CBZ, 3-OH-CBZ and 10-OH-CBZ were quantified in wastewater, surface water and drinking water. DiOH-CBZ showed the highest concentrations of all analaytes investigated and was found to be equally persistent as CBZ. In addition, several further degradation products of CBZ were found that could not be identified. The ELISA allowed the detection of diurnal and seasonal fluctuations of analyte concentrations in wastewater and surface water. The anthropogenic marker CBZ enabled to trace wastewater from the source to the receiving waters. Since neither sample pretreatment nor enrichment is necessary, the method is very fast and cost-effective. Only a small sample volume (less than 1 mL) is needed making this ELISA an appropriate high-throughput screening tool for environmental monitoring.

Koffein (1,3,7-Trimethylxanthin) und Coprostanol (5beta-cholestan-3beta-ol) wurden im Berliner Oberflächenwasser nachgewiesen. Ihre Konzentrationen korrelierten mit dem Verunreinigungsgrad der Proben, was nahelegt, dass sie sich als Marker für menschliche Aktivität eignen. Bemerkenswerterweise wurde Koffein in jeder einzelnen Oberflächenwasserprobe oberhalb der Bestimmungsgrenze von 0,025 µg/L gefunden. Um Oberflächenwasserproben in größeren Serien zu untersuchen, war die Entwicklung zweier neuer Methoden erforderlich: ein Immunoassay, basierend auf einem monoklonalen Antikörper für Koffein und eine dispersive flüssig-flüssig Mikroextraktionsmethode (DLLME), gefolgt von Flüssigkeitschromatographie gekoppelt mit Tandem-Massenspektrometrie (LC-MS/MS) für Coprostanol. Der entwickelte Koffein-Immunoassay zeigt die beste je erhaltene Nachweisgrenze für Koffein (0,001 µg/L), erlaubt Hochdurchsatz-Analysen und erfordert keine Probenvorbereitung. Der Assay wurde auch erfolgreich für die Messung von Koffein in Getränken, Haarwaschmitteln, Koffeintabletten und menschlichem Speichel angewendet. Antikörper gegen Coprostanol sind nicht kommerziell erhältlich. Eine neue Strategie Anti-Coprostanol-Antikörper zu generieren wurde erarbeitet, die eine analoge Verbindung – Isolithocholsäure (ILA) – als Hapten verwendet, mit der eine Gruppe von Mäusen immunisiert wurde. Ein polyklonales Anti-ILA-Serum wurde produziert, welches Coprostanol bindet, aber die niedrige Affinität erlaubte nicht den Aufbau eines Immunoassays, der die Messung von Umweltkonzentrationen des Anayten (im Bereich ng/L) zulässt. Spezifische Anti-ILA-Immunglobuline G wurden auch in den Faeces der Mäuse gefunden. Coprostanol wurde in den Wasserproben durch die Verwendung einer neuentwickelten LC-MS/MS-Methode unter APCI-Ionisation (atmospheric pressure chemical ionisation) gemessen. Konzentrationen oberhalb von 0,1 µg/L wurden nach Voranreicherung der Probe mittels DLLME bestimmt. / Caffeine (1,3,7-trimethylxanthine) and coprostanol (5beta-cholestan-3beta-ol) were detected in samples of Berlin’s surface water. Their concentrations correlated with the contamination status of the samples, suggesting their usefulness as markers of human activity. Remarkably, caffeine concentrations were always well above the limit of quantitation of 0.025 µg/L. In order to screen surface water samples in larger series, the development of two novel methods was required: a monoclonal antibody-based immunoassay for caffeine and a dispersive liquid-liquid microextraction (DLLME) method, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) for coprostanol. The caffeine immunoassay developed shows the best analytical limit of detection (LOD) obtained so far for caffeine (0.001 µg/L), allows high-throughput analysis, and does not require sample pre-treatment. The assay was also successfully employed to measure caffeine in beverages, shampoos, caffeine tab-lets, and human saliva. Antibodies to coprostanol are not commercially available. A new strategy to generate anti-coprostanol antibodies was elaborated using an analogous com-pound as hapten – isolithocholic acid (ILA) – and immunizing a group of mice. A polyclonal anti-ILA serum was produced, which binds coprostanol but the low affinity did not permit setting up an immunoassay to measure environmental concentrations of the analyte (in the range of ng/L). Specific anti-ILA immunoglobulin G were also found in the faeces of the immunized mice. Coprostanol was quantified in the water samples using a newly developed LC-MS/MS method using atmospheric pressure chemical ionisation (APCI). Concentrations above 0.1 µg/L were determined after sample preconcentration using DLLME. This extraction method also proved to be successful for enrichment of coprostanol-related compounds such as cholesterol, cholestanol, cholestanone, ergosterol, and stigmasterol.