Large volume (1,800 µL) injection HPLC/MS/MS for the quantitative determination of illicit drugs and human urinary biomarkers in municipal wastewater

A sensitive, selective, rapid analytical method based on large-volume injection (LVI) liquid chromatography/ tandem mass spectrometry was developed using commercially-available hardware that eliminates the need for either off-line or on-line solid phase extraction. Centrifugation followed by the direct injection of 1,800 µL was used for the quantification of illicit drugs, metabolites, and human urinary biomarkers in municipal wastewaters. The accuracy of the method as indicated by standard addition was calculated for analytes with concentrations ranging from 4 to 3,500,000 ng/L. The average precision of the method, as indicated by relative standard deviation is 7%. Detection limits range from 2.5 ng/L to 250 ng/L. As a demonstration of the method, the temporal trend in illicit drugs, selected metabolites and human urinary biomarkers was determined for 24-hr flow-normalized composite samples of raw influent collected from a single municipal wastewater treatment plant over the course of three weeks

Suspect and nontarget screening approaches to identify organic contaminant records in lake sediments

Sediment cores provide a valuable record of historical contamination, but so far, new analytical techniques such as high-resolution mass spectrometry (HRMS) have not yet been applied to extend target screening to the detection of unknown contaminants for this complex matrix. Here, a combination of target, suspect, and nontarget screening using liquid chromatography (LC)-HRMS/MS was performed on extracts from sediment cores obtained from Lake Greifensee and Lake Lugano located in the north and south of Switzerland, respectively. A suspect list was compiled from consumption data and refined using the expected method coverage and a combination of automated and manual filters on the resulting measured data. Nontarget identification efforts were focused on masses with Cl and Br isotope information available that exhibited mass defects outside the sample matrix, to reduce the effect of analytical interferences. In silico methods combining the software MOLGEN-MS/MS and MetFrag were used for direct elucidation, with additional consideration of retention time/partitioning information and the number of references for a given substance. The combination of all available information resulted in the successful identification of three suspect (chlorophene, flufenamic acid, lufenuron) and two nontarget compounds (hexachlorophene, flucofuron), confirmed with reference standards, as well as the tentative identification of two chlorophene congeners (dichlorophene, bromochlorophene) that exhibited similar time trends through the sediment cores. This study demonstrates that complementary application of target, suspect, and nontarget screening can deliver valuable information despite the matrix complexity and provide records of historical contamination in two Swiss lakes with previously unreported compounds

Interpreting Methamphetamine Levels in a High-Use Community

Illicit drug use is a largely hidden phenomenon and population measures are notoriously problematic. Reliable and valid data for local, regional and national public health and other interventions are needed. To address this information we examined temporal trends within and across weeks in methamphetamine (MA) in a single location in order to inform a sampling plan for understanding long-term trends in MA use based on sampling raw influent to waste water treatment plants. The measured concentrations in wastewater are used to estimate the total mass of MA consumed MA rather than the number of doses due to the uncertainty surrounding methamphetamine purity, mass of MA per dose, and the number of doses used per day. Results from a region with high levels of MA use indicate that MA levels do not differ significantly between weekdays and weekends (p=0.1), consistent with a predominately regular, daily use pattern use. The potential contribution of legal sales of d- and l-MA to the mass of MA consumed within the community was estimated to range from 3-8%. Limitations and uncertainties associated with estimating the mass of MA consumption include small contributions of prescription and over-the-counter drugs that are metabolized to MA as well as measurement and sampling variability.Keywords: Temporal patterns, Epidemiology wastewater, Methamphetamine (MA)Keywords: Temporal patterns, Epidemiology wastewater, Methamphetamine (MA

Fate of drugs during wastewater treatment

This is the post-print version of the final paper published in TrAC Trends in Analytical Chemistry. The published article is available from the link below. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. Copyright @ 2013 Elsevier B.V.Recent trends in the determination of pharmaceutical drugs in wastewaters focus on the development of rapid multi-residue methods. This review addresses recent analytical trends in drug determination in environmental matrices used to facilitate fate studies. Analytical requirements for further fate evaluation and tertiary process selection and optimization are also discussed.EPSRC, Northumbrian Water, Anglian Water, Severn Trent Water, Yorkshire Water, and United Utilities

Trace analysis of environmental matrices by large-volume injection and liquid chromatography-mass spectrometry

The time-honored convention of concentrating aqueous samples by solid-phase extraction (SPE) is being challenged by the increasingly widespread use of large-volume injection (LVI) liquid chromatography–mass spectrometry (LC–MS) for the determination of traces of polar organic contaminants in environmental samples. Although different LVI approaches have been proposed over the last 40 years, the simplest and most popular way of performing LVI is known as single-column LVI (SC-LVI), in which a large-volume of an aqueous sample is directly injected into an analytical column. For the purposes of this critical review, LVI is defined as an injected sample volume that is ≥10% of the void volume of the analytical column. Compared with other techniques, SC-LVI is easier to set up, because it requires only small hardware modifications to existing autosamplers and, thus, it will be the main focus of this review. Although not new, SC-LVI is gaining acceptance and the approach is emerging as a technique that will render SPE nearly obsolete for many environmental applications.In this review, we discuss: the history and development of various forms of LVI; the critical factors that must be considered when creating and optimizing SC-LVI methods; and typical applications that demonstrate the range of environmental matrices to which LVI is applicable, for example drinking water, groundwater, and surface water including seawater and wastewater. Furthermore, we indicate direction and areas that must be addressed to fully delineate the limits of SC-LVI

International Conference on Contaminated Sediments – ContaSed 2015 8–13 March 2015, Monte Verità, Ascona, Switzerland: Conference Report

About 80 participants from 22 countries from industry and academia gathered at the International Conference on Contaminated Sediments (ContaSed 2015) held at the Congressi Stefano Franscini (CSF), the conference center of ETH Zurich, located at Monte Verità, Ascona, Switzerland. ContaSed 2015 provided a platform for top experts as well as for junior researchers from different scientific disciplines to present recent results and novel approaches on the analysis, assessment and remediation of contaminated sediments. ContaSed 2015 served as a unique communication and discussion opportunity for environmental scientists with an emphasis on chemistry, sedimentology, ecotoxicology or remediation engineering

Screening of Lake Sediments for Emerging Contaminants by Liquid Chromatography Atmospheric Pressure Photoionization and Electrospray Ionization Coupled to High Resolution Mass Spectrometry

We developed a multiresidue method for the target and suspect screening of more than 180 pharmaceuticals, personal care products, pesticides, biocides, additives, corrosion inhibitors, musk fragrances, UV light stabilizers, and industrial chemicals in sediments. Sediment samples were freeze-dried, extracted by pressurized liquid extraction, and cleaned up by liquid–liquid partitioning. The quantification and identification of target compounds with a broad range of physicochemical properties (log <i>K</i>_ow 0–12) was carried out by liquid chromatography followed by electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) coupled to high resolution Orbitrap mass spectrometry (HRMS/MS). The overall method average recoveries and precision are 103% and 9% (RSD), respectively. The method detection limits range from 0.010 to 4 ng/g_dw, while limits of quantification range from 0.030 to 14 ng/g_dw. The use of APPI as an alternative ionization source helped to distinguish two isomeric musk fragrances by means of different ionization behavior. The method was demonstrated on sediment cores from Lake Greifensee located in northeastern Switzerland. The results show that biocides, musk fragrances, and other personal care products were the most frequently detected compounds with concentrations ranging from pg/g_dw to ng/g_dw, whereas none of the targeted pharmaceuticals were found. The concentrations of many urban contaminants originating from wastewater correlate with the highest phosphorus input into the lake as a proxy for treatment efficiency. HRMS enabled a retrospective analysis of the full-scan data acquisition allowing the detection of suspected compounds like quaternary ammonium surfactants, the biocide triclocarban, and the tentative identification of further compounds without reference standards, among others transformation products of triclosan and triclocarban

A mixture of environmental organic contaminants in lake sediments affects hatching from Daphniaresting eggs

Despite the relevance of resting eggs for ecology and evolution of many aquatic organisms and their exposure to contaminants accumulating in sediments, ecotoxicological studies using resting eggs are vastly underrepresented. The authors established a method to perform exposure assays with resting eggs produced by the Daphnia longispina species complex, key species in large lake ecosystems. A mixture of organic contaminants previously detected in sediments of Lake Greifensee was selected to test the potential effect of organic contaminants present in sediments on the hatching process. Resting eggs were exposed to a mix of 10 chemicals, which included corrosion inhibitors, biocides, pesticides, and personal care products, for a period of 15 d. Using an automated counting software, the authors found a significant increase in hatching success in the exposed resting eggs compared with controls. Such an effect has not yet been reported from ecotoxicological assays with resting eggs. Possible mechanistic explanations as well as the potential implications on the ecology and evolution of aquatic species that rely on a resting egg banks are discussed. Observed increased mortality and developmental abnormalities for hatchlings in the exposure treatments can be explained by toxic contaminant concentrations. The results of the present study highlight the need for additional studies assessing the effects of organic contaminants on resting egg banks and aquatic ecosystems

Glyphosate and terbuthylazine effects on soil functions, microbiome composition and crop performance

Herbicides are widely used for weed control in agriculture, though their fate and impact on non-target organisms like soil microbes and their function remain relatively unknown. A further complication is that herbicide effects vary depending on how they are applied and due to varying soil moisture conditions. In this study we tested the hypothesis that spraying glyphosate or terbuthylazine directly onto bare soil and when soil moisture is high would impact the soil microbial communities and their function most strongly. We measured similar amounts of glyphosate and terbuthylazine in soil whether the herbicides were directly applied to soil or first sprayed on the weed Chenopodium album and we found evidence for more rapid metabolization at high soil moisture. We found that the soil bacterial rather than the fungal community was mainly affected by a single application of the two tested herbicides. The identified shifts in community composition were independent of the modes of herbicide application but strongly dependent on soil moisture. We further found that herbicide applications only had a small impact on soil microbial function, which was approximated with analyses of the activities of N-β-acetylglucosaminidase, acid phosphatase and β-glucosidase enzymes in soil. Finally, we also assessed the postapplication performance of the subsequent crop and found that the herbicides did not affect maize height, chlorophyll content and biomass. Overall, our study revealed that a single application of herbicides in recommended doses had minor effects on the soil microbiome with a temporal and soil moisture dependency. The latter finding points out that to avoid repercussions on non-target organisms and soil function, key research needs to solve the context-dependency of rapid herbicide degradation in soil