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Persistent, Mobile, and Toxic (PMT) and very persistent and very mobile (vPvM) substances are a growing threat to water security and safety. Many of these substances are distinctively different from other more traditional contaminants in terms of their charge, polarity, and aromaticity. This results in distinctively different sorption affinities towards traditional sorbents such as activated carbon. Additionally, an increasing awareness on the environmental impact and carbon footprint of sorption technologies puts some of the more energy-intensive practices in water treatment into question. Commonly used approaches may thus need to be readjusted to become fit for purpose to remove some of the more challenging PMT and vPvM substances, including for example short chained per- and polyfluoroalkyl substances (PFAS). We here critically review the interactions that drive sorption of organic compounds to activated carbon and related sorbent materials and identify opportunities and limitations of tailoring activated carbon for PMT and vPvM removal. Other less traditional sorbent materials, including ion exchange resins, modified cyclodextrins, zeolites and metal-organic frameworks are then discussed for potential alternative or complementary use in water treatment scenarios. Sorbent regeneration approaches are evaluated in terms of their potential, considering reusability, potential for on-site regeneration, and potential for local production. In this context, we also discuss the benefits of coupling sorption to destructive technologies or to other separation technologies. Finally, we sketch out possible future trends in the evolution of sorption technologies for PMT and vPvM removal from water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The objective of this study was to investigate the transport behavior of two organic and persistent contaminants (alachlor and pentachlorobenzene) on Danube alluvial sediment in the absence and in the presence of microbially inoculated biochar produced at 400 °C and three hydrochars produced at 180, 200, and 220 °C. Stainless steel columns were used for the sorption experiments in nonequilibrium conditions. Obtained results were modeled using the advective-dispersive equation under nonequilibrium conditions. Transport of these compounds through the alluvial sediment column showed that the retention time increased with increasing molecular hydrophobicity. Inoculated biochar increases the retardation of both compounds: twofold for pentachlorobenzene compared with alachlor as a consequence of a higher hydrophobicity. Obtained results indicate that the highest biodegradation coefficient was observed for pentachlorobenzene (λ = 10) in alluvial sediment with addition of an inoculated hydrochar, which is assumed to be a consequence of biosorption. Moreover, all experiments on the columns indicate that the addition of inoculated chars yields a significantly higher R d coefficient for pentachlorobenzene than for alachlor. Bacterial counts increased in all of the column experiments, which indicates the successful adaptation of microorganisms to experimental conditions and their potential for the removal of a large number of organic pollutants. Thus, addition of inoculated chars to contaminated sediments has the potential as a remediation technique to inhibit the leaching of pollutants to groundwaters. Integr Environ Assess Manag 2023;19:933-942. © 2022 SETAC., (© 2022 SETAC.)

Purpose: Accumulating evidence from epidemiological studies that pediatric computed tomography (CT) examinations can be associated with a small but non-zero excess risk for developing leukemia or brain tumor highlights the need to optimize doses of pediatric CT procedures. Mandatory dose reference levels (DRL) can support reduction of collective dose from CT imaging. Regular surveys of applied dose-related parameters are instrumental to decide when technological advances and optimized protocol design allow lower doses without sacrificing image quality. Our aim was to collect dosimetric data to support adapting current DRL to changing clinical practice., Method: Dosimetric data and technical scan parameters from common pediatric CT examinations were retrospectively collected directly from Picture Archiving and Communication Systems (PACS), Dose Management Systems (DMS), and Radiological Information Systems (RIS)., Results: We collected data from 17 institutions on 7746 CT series from the years 2016 to 2018 from examinations of the head, thorax, abdomen, cervical spine, temporal bone, paranasal sinuses and knee in patients below 18 years of age. Most of the age-stratified parameter distributions were lower than distributions from previously-analyzed data from before 2010. Most of the third quartiles were lower than German DRL at the time of the survey., Conclusions: Directly interfacing PACS, DMS, and RIS installations allows large-scale data collection but relies on high data-quality at the documentation stage. Data should be validated by expert knowledge or guided questionnaires. Observed clinical practice in pediatric CT imaging suggests lowering some DRL in Germany is reasonable., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Climate change, biodiversity loss, and chemical pollution are planetary-scale emergencies requiring urgent mitigation actions. As these "triple crises" are deeply interlinked, they need to be tackled in an integrative manner. However, while climate change and biodiversity are often studied together, chemical pollution as a global change factor contributing to worldwide biodiversity loss has received much less attention in biodiversity research so far. Here, we review evidence showing that the multifaceted effects of anthropogenic chemicals in the environment are posing a growing threat to biodiversity and ecosystems. Therefore, failure to account for pollution effects may significantly undermine the success of biodiversity protection efforts. We argue that progress in understanding and counteracting the negative impact of chemical pollution on biodiversity requires collective efforts of scientists from different disciplines, including but not limited to ecology, ecotoxicology, and environmental chemistry. Importantly, recent developments in these fields have now enabled comprehensive studies that could efficiently address the manifold interactions between chemicals and ecosystems. Based on their experience with intricate studies of biodiversity, ecologists are well equipped to embrace the additional challenge of chemical complexity through interdisciplinary collaborations. This offers a unique opportunity to jointly advance a seminal frontier in pollution ecology and facilitate the development of innovative solutions for environmental protection., (© 2023 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

Remediation of residually contaminated soils remains a widespread problem. Biochar can immobilize polycyclic aromatic hydrocarbons (PAH). However, studies on its ability to immobilize PAH and N, S, and O substituted PAH (hetero-PAH) in real soils, and benchmarking with commercial activated carbon are missing. Here, we compared the ability of pristine biochar (BC), steam-activated biochar (SABC), and commercial activated carbon (AC) to immobilize PAH and hetero-PAH. The three carbons were tested on soils from four different contaminated sites in Austria. Different amendment rates (w/w) of the carbons were investigated (BC: 1.0, 2.5, and 5%; SABC: 0.5, 1.0, and 2.0%; AC: 1%) in batch experiments to cover meaningful ranges in relation to their performance. SABC performed better than AC, removing at least 80% PAH with the lowest application rate of 0.5%, and achieving a complete removal at an application rate of 1.0%. BC performed slightly worse but still acceptable in residually contaminated soils (40 and 100% removal at 1 and 5% amendment, respectively). The ability of BC and SABC to immobilize PAH decreased as the PAH-molar volume increased. PAH with three or more rings were preferentially removed by AC compared to SABC or BC. This can be explained by the difference in pore size distribution of the carbons which could limit the accessibility of PAH and hetero-PAH to reach sorption sites for π- π electron donor-acceptor interactions, which drive PAH and hetero-PAH sorption to carbons. Column percolation tests confirmed the results obtained in batch tests, indicating, that decisions for soil remediation can be derived from simpler batch experiments. In soil samples with 1% BC, a reduction of over 90% in the total concentration of PAH in the leached water was observed. Overall, BC and SABC were demonstrated to be valid substitutes for AC for stabilizing residually contaminated soils., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

In Europe alone, >200 million m 3 of river sediments are dredged each year, part of which are contaminated to such an extent that they have to be landfilled. This study compares the use of biochar and hydrochar for the remediation of sediment contaminated with pentachlorobenzene, hexachlorobenzene, lindane, trifluralin, alachlor, simazine, and atrazine with the motivation to make sediments contaminated by such priority substances usable as arable land for growing energy crops. Biochar and hydrochar originating from Miscanthus giganteus and Beta vulgaris shreds were compared for their potential to reduce contaminant associated risk in sediments. Specifically, by investigating the effects of sorbent amendment rate (1, 5, and 10 %) and incubation time (14, 30, and 180 d) on contaminant bioaccessibility, toxicity to the bacteria Vibrio fischeri, as well as toxicity and plant uptake in Zea mays. Biochar reduced contaminant bioaccessibility up to five times more than hydrochar. The bioaccessibility of contaminants decreased up to sevenfold with increasing incubation time, indicating that the performance of carbonaceous sorbents may be underestimated in short-term lab experiments. Biochar reduced contaminants toxicity to Vibrio fischeri, whereas hydrochar was itself toxic to the bacteria. Toxicity to Zea mays was determined by contaminant bioaccessibility but also sorbent feedstock with cellulose rich Beta vulgaris based sorbents exhibiting toxic effects. The plant uptake of all contaminants decreased after sorbent amendment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Biochars can remove potentially toxic elements, such as inorganic mercury [Hg(II)] from contaminated waters. However, their performance in complex water matrices is rarely investigated, and the combined roles of natural organic matter (NOM) and ionic composition in the removal of Hg(II) by biochar remain unclear. Here, we investigate the influence of NOM and major ions such as chloride (Cl - ), nitrate (NO 3 - ), calcium (Ca 2+ ), and sodium (Na + ) on Hg(II) removal by a wood-based biochar (SWP700). Multiple sorption sites containing sulfur (S) were located within the porous SWP700. In the absence of NOM, Hg(II) removal was driven by these sites. Ca 2+ bridging was important in enhancing removal of negatively charged Hg(II)-chloro complexes. In the presence of NOM, formation of soluble Hg-NOM complexes (as seen from speciation calculations), which have limited access to biochar pores, suppressed Hg(II) removal, but Cl - and Ca 2+ could still facilitate it. The ability of Ca 2+ to aggregate NOM, including Hg-NOM complexes, promoted Hg(II) removal from the dissolved fraction (<0.45 μm). Hg(II) removal in the presence of Cl - followed a stepwise mechanism. Weakly bound oxygen functional groups in NOM were outcompeted by Cl - , forming smaller-sized Hg(II)-chloro complexes, which could access additional intraparticle sorption sites. Therein, Cl - was outcompeted by S, which finally immobilized Hg(II) in SWP700 as confirmed by extended X-ray absorption fine structure spectroscopy. We conclude that in NOM containing oxic waters, with relatively high molar ratios of Cl - : NOM and Ca 2+ : NOM, Hg(II) removal can still be effective with SWP700.

Permanently charged and ionizable organic compounds (IOC) are a large and diverse group of compounds belonging to many contaminant classes, including pharmaceuticals, pesticides, industrial chemicals, and natural toxins. Sorption and mobility of IOCs are distinctively different from those of neutral compounds. Due to electrostatic interactions with natural sorbents, existing concepts for describing neutral organic contaminant sorption, and by extension mobility, are inadequate for IOC. Predictive models developed for neutral compounds are based on octanol-water partitioning of compounds ( K ow ) and organic-carbon content of soil/sediment, which is used to normalize sorption measurements ( K OC ). We revisit those concepts and their translation to IOC ( D ow and D OC ) and discuss compound and soil properties determining sorption of IOC under water saturated conditions. Highlighting possible complementary and/or alternative approaches to better assess IOC mobility, we discuss implications on their regulation and risk assessment. The development of better models for IOC mobility needs consistent and reliable sorption measurements at well-defined chemical conditions in natural porewater, better IOC-, as well as sorbent characterization. Such models should be complemented by monitoring data from the natural environment. The state of knowledge presented here may guide urgently needed future investigations in this field for researchers, engineers, and regulators.

Wildfires produce large amounts of pyrogenic carbon (PyC), including charcoal, known for its chemical recalcitrance and sorption affinity for organic molecules. Wildfire-derived PyC can be transported to fluvial networks. Here it may alter the dissolved organic matter (DOM) concentration and composition as well as microbial biofilm functioning. Effects of PyC on carbon cycling in freshwater ecosystems remain poorly investigated. Employing in-stream flumes with a control versus treatment design (PyC pulse addition), we present evidence that field-aged PyC inputs to rivers can increase the dissolved organic carbon (DOC) concentration and alter the DOM composition. DOM fluorescence components were not affected by PyC. The in-stream DOM composition was altered due to leaching of pyrogenic DOM from PyC and possibly concurrent sorption of riverine DOM to PyC. Decreased DOM aromaticity indicated by a lower SUVA 245 (-0.31 unit) and a higher pH (0.25 unit) was associated with changes in enzymatic activities in benthic biofilms, including a lower recalcitrance index (β-glucosidase/phenol oxidase), suggesting preferential usage of recalcitrant over readily available DOM by biofilms. The deposition of particulate PyC onto biofilms may further modulate the impacts of PyC due to direct contact with the biofilm matrix. This study highlights the importance of PyC for in-stream biogeochemical organic matter cycling in fire-affected watersheds., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

A potential risk from human uptake of microplastics is the release of plastics-associated xenobiotics, but the key physicochemical properties of microplastics controlling this process are elusive. Here, we show that the gastrointestinal bioaccessibility, assessed using an in vitro digestive model, of two model xenobiotics (pyrene, at 391-624 mg/kg, and 4-nonylphenol, at 3054-8117 mg/kg) bound to 18 microplastics (including pristine polystyrene, polyvinyl chloride, polyethylene terephthalate, polypropylene, thermoplastic polyurethane, and polyethylene, and two artificially aged samples of each polymer) covered wide ranges: 16.1-77.4% and 26.4-83.8%, respectively. Sorption/desorption experiments conducted in simulated gastric fluid indicated that structural rigidity of polymers was an important factor controlling bioaccessibility of the nonpolar, nonionic pyrene, likely by inducing physical entrapment of pyrene in porous domains, whereas polarity of microplastics controlled bioaccessibility of 4-nonylphenol, by regulating polar interactions. The changes of bioaccessibility induced by microplastics aging corroborated the important roles of polymeric structures and surface polarity in dictating sorption affinity and degree of desorption hysteresis, and consequently, gastrointestinal bioaccessibility. Variance-based global sensitivity analysis using a deep learning neural network approach further revealed that micropore volume was the most important microplastics property controlling bioaccessibility of pyrene, whereas the O/C ratio played a key role in dictating the bioaccessibility of 4-nonylphenol in the gastric tract.

Dissolved organic matter (DOM) is ubiquitous in aquatic environments where it interacts with a variety of particles including carbonaceous materials (CMs). The complexity of both DOM and the CMs makes DOM-CM interactions difficult to predict. In this study we have identified the preferential sorption of specific DOM fractions as being dependent on their aromaticity and molecular weight, as well as on the surface properties of the CMs. This was achieved by conducting sorption batch experiments with three types of DOM (humic acid, Suwannee River natural organic matter, and a compost extract) and three types of CMs (graphite, carbon nanotubes, and biochar) with different geometries and surface complexities. The non-adsorbed DOM fraction was analyzed by size exclusion chromatography and preferentially sorbed molecular weight fractions were analyzed by UV/vis and fluorescence spectroscopy. All three sorbent types were found to preferentially sorb aromatic DOM fractions, but DOM fractionation depended on the particular combination of sorbent and sorbate characteristics. Single-walled carbon nanotubes only sorbed the smaller molecular weight fractions (<1 kDa). The sorption of smaller DOM fractions was not accompanied by a preference for less aromatic compounds, contrary to what was suggested in previous studies. While graphite preferentially sorbed the most aromatic DOM fraction (1-3 kDa), the structural heterogeneity of biochar resulted in reduced selectivity, sorbing all DOM > 1 kDa. The results explain the lack of correlation found in previous studies between the amount of aromatic carbon in a bulk DOM and its sorption coefficient. DOM sorption by CMs was generally controlled by DOM aromaticity but complex sorbent surfaces with high porosity, curvatures and functional groups strongly reduced the importance of aromaticity.

Implementing advanced wastewater treatment (WWT) to eliminate organic micropollutants (OMPs) is a necessary step to protect vulnerable freshwater ecosystems and water resources. To this end, sorption of OMP by activated carbon (AC) is one viable technology among others. However, conventional AC production based on fossil precursor materials causes environmental pollution, including considerable emissions of greenhouse gases. In this study, we produced activated biochar (AB) from wood and woody residues by physical activation and evaluated their capability to eliminate OMPs in treated wastewater. Activated biochar produced under optimized conditions sorbed 15 model OMPs, of which most were dissociated at circumneutral pH, to the same or higher extent than commercial AC used as a reference. While wood quality played a minor role, the dosage of the activation agent was the main parameter controlling the capacity of ABs to eliminate OMP. Our results highlight the possibility for local production of AB from local wood or woody residues as a strategy to improve WWT avoiding negative side effects of conventional AC production., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

The exponential growth in the use of motor vehicles is a key contributor to freshwater degradation. Current remediation techniques require prohibitively expensive contaminant treatment and extraction. Biochar represents an inexpensive option to ameliorate contaminants from motorway runoff. Biochar from Norway spruce (Picea abies (L.) Karst.) was produced under fast pyrolysis-gasification (450-500 °C for 90 s) and amended with wood ash and basaltic rock dust to evaluate sorption of Pb, Cu, Zn and Cd. The column study, designed to mimic field conditions, confirmed that unamended biochar can bind contaminants for short periods, but that the addition of amendments, particularly wood ash, significantly improves contaminant removal. Wood ash-amended biochar removed 98-100% of all contaminants during the study, driven by pH (r = 0.73-0.74; p < 0.01 dependent on metal species) and phosphorus levels causing precipitation (r = 0.47-0.59; p < 0.01, dependent on metal species). The contaminants' progression through the biochar subsections in the column indicated that increasing the thickness of the biochar layer increased contaminant residence time and removal.

Most contaminants of emerging concern are polar and/or ionizable organic compounds, whose removal from engineered and environmental systems is difficult. Carbonaceous sorbents include activated carbon, biochar, fullerenes, and carbon nanotubes, with applications such as drinking water filtration, wastewater treatment, and contaminant remediation. Tools for predicting sorption of many emerging contaminants to these sorbents are lacking because existing models were developed for neutral compounds. A method to select the appropriate sorbent for a given contaminant based on the ability to predict sorption is required by researchers and practitioners alike. Here, we present a widely applicable deep learning neural network approach that excellently predicted the conventionally used Freundlich isotherm fitting parameters log K F and n ( R 2 > 0.98 for log K F , and R 2 > 0.91 for n ). The neural network models are based on parameters generally available for carbonaceous sorbents and/or parameters freely available from online databases. A freely accessible graphical user interface is provided.

Soot is an important carbonaceous nanoparticle (CNP) frequently found in natural environments. Its entry into surface waters can occur directly via surface runoff or infiltration, as well as via atmospheric deposition. Pristine soot is likely to rapidly undergo aggregation and subsequent sedimentation in aquatic environments. Further, soot can sorb a variety of organic contaminants, such as S-metolachlor (log KD = 3.25 ± 0.12). During atmospheric transport, soot can be chemically transformed by reactive oxygen species including NO2. The presence of natural organic matter (NOM) in surface waters can further affect the aquatic fate of soot. To better understand the processes driving the fate of soot and its interactions with contaminants, pristine and NO2-transformed model soot suspensions were investigated in the presence and absence of NOM. NO2-oxidized soot showed a smaller particle size, a higher number of particles remaining in suspension, and a decreased sorption of S-metolachlor (log KD = 2.47 ± 0.40). In agreement with findings for other CNPs, soot stability against aggregation was increased for both pristine and NO2 transformed soot in the presence of NOM.

The beneficial properties of biochar have led to its increasing application to soils for environmental management. Despite its stability in soil, biochar can physically disintegrate into smaller particles, which can then be relocated from the application area. Biochar transport is strongly dependent on the biochar particle size and aggregation, with the extent of aggregation depending on the chemistry of the soil pore water. Biochar has a strong sorption affinity for polyaromatic hydrocarbons (PAHs) such as pyrene, which can also affect its transport. We therefore investigated biochar particle aggregation in solutions of different ionic strengths (ultrapure water, 0.01 M CaCl2, and 0.1 M CaCl2) with suspensions of biochar particles, and with suspensions of biochar particles loaded with pyrene (0.2 and 3.6 g kg-1). Increasing the pyrene concentration in ultrapure water resulted in an increase in the biochar particle size, an effect that was more pronounced following equilibration for 28 days than following equilibration for only 24 hours. Biochar particle aggregation in solutions containing both pyrene and 0.01 M CaCl2 was greatly enhanced compared to aggregation in similar solutions with no pyrene. However, the influence of pyrene became negligible at high CaCl2 concentrations (0.1 M CaCl2). To determine the fate of biochar in soil, both the presence of PAHs and the influence of the pore water's ionic strength therefore need to be taken into account.

Plastics are now found in all natural environments including soil. The effects of microplastics in terrestrial systems, however, remain largely unexplored. Polyethylene is one of the mass-manufactured polymers found in terrestrial environments. It is used in many different sectors, for example in agricultural mulches, composite materials, and packaging. The presence of microplastics in soil, including polyethylene, can affect the transport of hydrophobic organic pollutants including pesticides. The objective of this study was to investigate the influence of polyethylene microplastics (<250 μm) on the transport of two selected organic plant-protection agents (atrazine and 4-(2,4-dichlorophenoxy) butyric acid) in soil under different aqueous conditions, using inverse liquid chromatography. The distribution coefficients for the sorbates that were sorbed to pure polyethylene microplastic were found to be significantly smaller than those for the sorbates sorbed to pure soil. The addition of 10% (w/w) polyethylene to the soil therefore led to an overall reduction in sorption, but the sorption trends due to variations in pH and ionic strength were not affected. The results imply that the presence of polyethylene microplastics in soil may therefore increase the mobility of organic contaminants by reducing the sorption capacity of natural soils, which must be validated by further research., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Amendment with biochar and/or compost has been proposed as a strategy to remediate soil contaminated with low levels of polycyclic aromatic hydrocarbons. The strong sorption potential of biochar can help sequestering contaminants while the compost may promote their degradation. An improved understanding of how sorption evolves upon soil amendment is an essential step towards the implementation of the approach. The present study reports on the sorption of pyrene to two soils, four biochars and one compost. Detailed isotherm analyzes across a wide range of concentration confirmed that soil amendments can significantly increase the sorption of pyrene. Comparisons of data obtained by a classical batch and a passive sampling method suggest that dissolved organic matter did not play a significant role on the sorption of pyrene. The addition of 10% compost to soil led to a moderate increase in sorption (<2-fold), which could be well predicted based on measurements of sorption to the individual components. Hence, our result suggest that the sorption of pyrene to soil and compost can be relatively well approximated by an additive process. The addition of 5% biochar to soil (with or without compost) led to a major increase in the sorption of pyrene (2.5-4.7-fold), which was, however, much smaller than that suggested based on the sorption measured on the three individual components. Results suggest that the strong sorption to the biochar was attenuated by up to 80% in the presence of soil and compost, much likely due to surface and pore blockage. Results were very similar in the two soils considered, and collectively suggest that combined amendments with compost and biochar may be a useful approach to remediate soils with low levels of contamination. Further studies carried out in more realistic settings and over longer periods of time are the next step to evaluate the long term viability of remediation approaches based on biochar amendments., Competing Interests: Melanie Kah is an Academic Editor for PeerJ.

Diffusely contaminated soils often remain untreated as classical remediation approaches would be disproportionately expensive. Adding compost can accelerate the biodegradation of organic contaminants and adding biochar can immobilize contaminants through sorption. The combined use of compost and biochar to reduce polycyclic aromatic hydrocarbon (PAH) and NSO-substituted PAH contamination has, however, not previously been systematically investigated. We have therefore investigated the processes involved (i) through sorption batch experiments, (ii) by monitoring changes in bacterial, fungal and archaeal communities using denaturing gradient gel electrophoresis, and (iii) through degradation experiments with fluorene, phenanthrene, pyrene, carbazole, dibenzothiophene, and dibenzofuran. Sorption coefficients for organic contaminants in soils increased tenfold following 10% compost addition and up to a hundredfold with further addition of 5% biochar. The rate of PAH and NSO-PAH degradation increased up to twofold following compost addition despite increased sorption, probably due to the introduction of additional microbial species into the autochthonous soil communities. In contrast, degradation of PAHs and NSO-PAHs in soil-compost-biochar mixtures slowed down up to tenfold due to the additional sorption, although some degradation still occurred. The combined use of biochar and compost may therefore provide a strategy for immobilizing PAHs and NSO-PAHs and facilitating degradation of remaining accessible contaminant fractions., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The sorption of ionic and ionizable organic compounds (IOCs) (e.g., pharmaceuticals and pesticides) on carbonaceous materials plays an important role in governing the fate, transport and bioavailability of IOCs. The paradigms previously established for the sorption of neutral organic compounds do not always apply to IOCs and the importance of accounting for the particular sorption behavior of IOCs is being increasingly recognized. This review presents the current state of knowledge and summarizes the recent advances on the sorption of IOCs to carbonaceous sorbents. A broad range of sorbents were considered to evaluate the possibility to read across between fields of research that are often considered in isolation (e.g., carbon nanotubes, graphene, biochar, and activated carbon). Mechanisms relevant to IOCs sorption on carbonaceous sorbents are discussed and critically evaluated, with special attention being given to emerging sorption mechanisms including low-barrier, charge-assisted hydrogen bonds and cation-π assisted π-π interactions. The key role played by some environmental factors is also discussed, with a particular focus on pH and ionic strength. Overall the review reveals significant advances in our understanding of the interactions between IOCs and carbonaceous sorbents. In addition, knowledge gaps are identified and priorities for future research are suggested., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The study investigates the role of biochar and/or compost in mitigating the toxic effects of pyrene in soils using reproduction of nematodes and porewater concentration as measures of pyrene toxicity and bioavailability, respectively. Two soils were spiked with increasing levels of pyrene to achieve a concentration-response relationship for the reproduction of Caenorhabditis elegans. The observed EC50 values (pyrene concentration causing 50% inhibition of reproduction) were 14mg/kg and 31mg/kg (dry mass) for these soils, corresponding to equilibrium porewater concentrations of 37μg/L and 47μg/L, respectively. Differences in organic carbon content were not sufficient to explain the variability in toxicity between the different soils. Soils causing a significant inhibition of reproduction were further amended with 10%-compost, 5%-biochar, or both, and the effects on reproduction and porewater concentration determined. Combined addition of compost and biochar was identified as the most effective strategy in reducing pyrene concentration in soil porewater, which was also partly reflected in soil toxicity. However, porewater concentrations predicted only 52% of pyrene toxicity to nematodes, pointing to particle-bound or dietary exposure pathways. Capsule: Amending pyrene-spiked soil with biochar and compost effectively reduced pyrene porewater concentrations and toxicity to nematodes, which were significantly related., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The influence of ageing on biochar properties has been investigated by comparing three fresh biochars with biochars artificially aged by either H 2 O 2 thermal oxidation or horseradish peroxidase enzymatic oxidation. In addition, a field-aged counterpart for one of the biochars was recovered from an agricultural field site, four years after application. Biochar properties, including surface areas and pore volumes (derived by N 2 and CO 2 physisorption) and elemental compositions, showed only minor changes following both artificial and field ageing, indicating high biochar stability. Concentrations of the 16 US EPA PAHs were measured in all of the biochars and a contaminant trap was used to investigate the effect of ageing on their bioaccessibility. The concentrations of total and bioaccessible PAHs ranged from 4.4 to 22.6 mg kg -1 and 0.0 to 9.7 mg kg -1 , respectively. Concentrations of the 16 US EPA PAHs decreased following field ageing, but the proportion of low molecular weight PAHs increased. The observed changes in PAH composition with field ageing can be explained by uptake from the surrounding soil and intra-biochar transfer processes. To better understand changes in PAH composition with ageing, an additional broad range of alkylated PAHs was also analyzed in selected samples. Our results show that the tested artificial ageing protocols are unable to approximate the changes in PAH composition resulting from field ageing. Nevertheless, total and bioaccessible PAH concentrations decreased for both artificially and field-aged biochars, indicating that biochars release PAHs when they are freshly produced and that the risk of PAH release decreases with ageing.

The surface area and pore volume of carbonaceous materials, which are commonly determined by N 2 and/or CO 2 gas-physisorption, are important parameters when describing environmental processes such as adsorption. Their measurement requires prior degassing of samples, which can change the nature of the material. Current guidelines for biochar characterization recommend different degassing temperatures. To investigate how degassing temperatures affect gas-physisorption we systematically degassed a range of materials (four biochars, carbon nanotubes, and Al 2 O 3 reference material) at different temperatures (105, 150, 200, 250 and 300°C; for ≥14h each). Degassing temperatures had no effect on Al 2 O 3 or carbon nanotubes but the measured surface areas and pore volumes of biochars increased by up to 300% with degassing temperature. An equation is presented for predicting surface area obtained at different degassing temperatures. Elemental analysis and results from sorption batch experiments suggest that surface area and pore volume may increase as biochar components volatilize during degassing. Our results showed that degassing temperatures change material properties and influence gas-physisorption measurements, and therefore need to be standardized. These results may also apply to the characterization of other complex materials, including carbon nanotubes coated with natural organic matter and fouled activated carbon., (Copyright © 2016 Elsevier B.V. All rights reserved.)

So far, in sports drug testing compounds of different classes are processed and measured using different screening procedures. The constantly increasing number of samples in doping analysis, as well as the large number of substances with doping related, pharmacological effects require the development of even more powerful assays than those already employed in sports drug testing, indispensably with reduced sample preparation procedures. The analysis of native urine samples after direct injection provides a promising analytical approach, which thereby possesses a broad applicability to many different compounds and their metabolites, without a time-consuming sample preparation. In this study, a novel multi-target approach based on liquid chromatography and high resolution/high accuracy mass spectrometry is presented to screen for more than 200 analytes of various classes of doping agents far below the required detection limits in sports drug testing. Here, classic groups of drugs as diuretics, stimulants, β 2 -agonists, narcotics and anabolic androgenic steroids as well as various newer target compounds like hypoxia-inducible factor (HIF) stabilizers, selective androgen receptor modulators (SARMs), selective estrogen receptor modulators (SERMs), plasma volume expanders and other doping related compounds, listed in the 2016 WADA prohibited list were implemented. As a main achievement, growth hormone releasing peptides could be implemented, which chemically belong to the group of small peptides (<2kDa) and are commonly determined by laborious and time-consuming stand-alone assays. The assay was fully validated for qualitative purposes considering the parameters specificity, robustness (rRT: <2%), intra- (CV: 1.7-18.4 %) and inter-day precision (CV: 2.3-18.3%) at three concentration levels, linearity (R 2 >0.99), limit of detection (0.1-25ng/mL; 3'OH-stanozolol glucuronide: 50pg/mL; dextran/HES: 10μg/mL) and matrix effects., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Sewage sludge (50% mineral), manure (29%) and wood (<1%) were pyrolyzed at 200, 350 and 500°C with the aim to study the characteristics and sorption potential of materials undergoing pyrolysis across a wide range of mineral contents. A commercial plant-derived biochar (41% mineral) was also considered. The materials were extensively characterized and tested for their sorption towards the model sorbates benzene, naphthalene and pyrene. Plant-derived materials, regardless of their mineral content, developed micropores causing size exclusion of pyrene. Changes in properties and sorption behavior upon pyrolysis were generally consistent for the manure and wood series. A single regression equation developed on our data (including the sorbate hydrophobicity and sorbent polarity) provided excellent prediction of previously reported changes in sorption upon pyrolysis across a wide range of mineral content (up to 500°C). The sewage sludge series, however, followed a particular behavior, possibly due to very high mineral content (up to 67%)., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Approaches based on the octanol-water partition coefficient are commonly used to describe sorption of neutral organic compounds in environmental systems, but they are not suitable for organic acids, which can dissociate to form anions. We here investigate the applicability of an alternative approach based on the pH-dependent distribution ratio (DOW) to describe sorption of aromatic acids to sorbents representing different degrees of carbonization. Sorption isotherms for four structurally similar acids ((2,4-dichlorophenoxy)acetic acid (2,4-D), 4-chloro-2-15 methylphenoxy)acetic acid (MCPA), 4-(2,4-dichlorophenoxy)butanoic16 acid (2,4-DB), and 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan)) were measured for 15 sorbents: fresh and carbonized wood shavings, pig manure, sewage sludge, carbon nanotubes, and activated carbon. Dissociation greatly affected the sorption of all acids. Sorption coefficients measured in the high pH range indicated that sorption of the anions ranged over several orders of magnitude and should not be neglected. Sorption trends for all sorbates and carbonized sorbents could be very well described by a single regression equation that included DOW of the sorbate and the specific surface area of the sorbent (R(2) > 0.89).

2-Phenylethanamine (phenethylamine, PEA) represents the core structure of numerous drugs with stimulant-like properties and is explicitly featured as so-called specified substance on the World Anti-Doping Agency (WADA) Prohibited List. Due to its natural occurrence in humans as well as its presence in dietary products, studies concerning the ability of test methods to differentiate between an illicit intake and the renal elimination of endogenously produced PEA were indicated. Following the addition of PEA to the Prohibited List in January 2015, retrospective evaluation of routine doping control data of 10 190 urine samples generated by combined gas chromatography-mass spectrometry and nitrogen phosphorus-specific detection (GC-MS/NPD) was performed. Signals for PEA at approximate concentrations > 500 ng/mL were observed in 31 cases (0.3%), which were subjected to a validated isotope-dilution liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS) test method for accurate quantification of the target analyte. Further, using elimination study urine samples collected after a single oral administration of 250 mg of PEA hydrochloride to two healthy male volunteers, two tentatively identified metabolites of PEA were observed and evaluated concerning their utility as discriminative markers for PEA intake. The ID-LC-MS/MS approach was extended to allow for the simultaneous detection of PEA and 2-(3-hydroxyphenyl)acetamide sulfate (M1), and concentration ratios of M1 and PEA were calculated for elimination study urine samples and a total of 205 doping control urine samples that returned findings for PEA at estimated concentrations of 50-2500 ng/mL. Urine samples of the elimination study with PEA yielded concentration ratios of M1/PEA up to values of 9.4. Notably, the urinary concentration of PEA did increase with the intake of PEA only to a modest extent, suggesting a comprehensive metabolism of the orally administered substance. Conversely, doping control urine samples with elevated (>50 ng/mL) amounts of PEA returned quantifiable concentrations of M1 only in 3 cases, which yielded maximum ratios of M1/PEA of 0.9, indicating an origin of PEA other than an orally ingested drug formulation. Consequently, the consideration of analyte abundance ratios (e.g. M1/PEA) is suggested as a means to identify the use of PEA by athletes, but further studies to support potential decisive criteria are warranted., (Copyright © 2015 John Wiley & Sons, Ltd.)

In the field of LC-MS, reversed phase liquid chromatography is the predominant method of choice for the separation of prohibited substances from various classes in sports drug testing. However, highly polar and charged compounds still represent a challenging task in liquid chromatography due to their difficult chromatographic behavior using reversed phase materials. A very promising approach for the separation of hydrophilic compounds is hydrophilic interaction liquid chromatography (HILIC). Despite its great potential and versatile advantages for the separation of highly polar compounds, HILIC is up to now not very common in doping analysis, although most manufacturers offer a variety of HILIC columns in their portfolio. In this study, a novel multi-target approach based on HILIC high resolution/high accuracy mass spectrometry is presented to screen for various polar stimulants, stimulant sulfo-conjugates, glycerol, AICAR, ethyl glucuronide, morphine-3-glucuronide, and myo-inositol trispyrophosphate after direct injection of diluted urine specimens. The usage of an effective online sample cleanup and a zwitterionic HILIC analytical column in combination with a new generation Hybrid Quadrupol-Orbitrap® mass spectrometer enabled the detection of highly polar analytes without any time-consuming hydrolysis or further purification steps, far below the required detection limits. The methodology was fully validated for qualitative and quantitative (AICAR, glycerol) purposes considering the parameters specificity; robustness (rRT < 2.0%); linearity (R > 0.99); intra- and inter-day precision at low, medium, and high concentration levels (CV < 20%); limit of detection (stimulants and stimulant sulfo-conjugates < 10 ng/mL; norfenefrine; octopamine < 30 ng/mL; AICAR < 10 ng/mL; glycerol 100 μg/mL; ETG < 100 ng/mL); accuracy (AICAR 103.8-105.5%, glycerol 85.1-98.3% at three concentration levels) and ion suppression/enhancement effects.

Since January 2014, the anti-anginal drug trimetazidine [1-(2,3,4-trimethoxybenzyl)-piperazine] has been classified as prohibited substance by the World Anti-Doping Agency (WADA), necessitating specific and robust detection methods in sports drug testing laboratories. In the present study, the implementation of the intact therapeutic agent into two different initial testing procedures based on gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) is reported, along with the characterization of urinary metabolites by electrospray ionization-high resolution/high accuracy (tandem) mass spectrometry. For GC-MS analyses, urine samples were subjected to liquid-liquid extraction sample preparation, while LC-MS/MS analyses were conducted by established 'dilute-and-inject' approaches. Both screening methods were validated for trimetazidine concerning specificity, limits of detection (0.5-50 ng/mL), intra-day and inter-day imprecision (<20%), and recovery (41%) in case of the GC-MS-based method. In addition, major metabolites such as the desmethylated trimetazidine and the corresponding sulfoconjugate, oxo-trimetazidine, and trimetazidine-N-oxide as identified in doping control samples were used to complement the LC-MS/MS-based assay, although intact trimetazidine was found at highest abundance of the relevant trimetazidine-related analytes in all tested sports drug testing samples. Retrospective data mining regarding doping control analyses conducted between 1999 and 2013 at the Cologne Doping Control Laboratory concerning trimetazidine revealed a considerable prevalence of the drug particularly in endurance and strength sports accounting for up to 39 findings per year., (Copyright © 2014 John Wiley & Sons, Ltd.)

Purpose: The desire to increase the athletic performance, to 'optimize' an individual's appearance, and to complement but also to arguably substitute exercise by means of drugs and drug candidates has generated a considerable (illicit) market for compounds such as anabolic-androgenic steroids, stimulants, growth promoting peptide hormones, and so on. Genuinely developed for therapeutic use, their abuse/misuse generates enormous health risks, which has necessitated comprehensive controls of compound trafficking by customs and anti-doping authorities., Methods: From 2012 to 2013, the Bureau of Customs Investigation confiscated products containing anabolic-androgenic steroids (AAS; 259 kg), stimulants (13 kg), selective estrogen receptor modulators (SERMs; 24 kg), and human growth hormone (hGH; 3500 ampules). In cooperation with the Bureau and under the umbrella of the European Monitoring Center for Emerging Doping Agents (EuMoCEDA), the Cologne Anti-Doping Laboratory analyzed an additional 337 (black market) products between 2010 and 2013, allowing to monitor developments in drug use and, hence, the anticipation of new challenges in sports drug testing. Main tools utilized in characterizing confiscated materials were liquid chromatography-high resolution mass spectrometry (LC-HRMS), gas chromatography-high resolution mass spectrometry (GC-HRMS), and polyacrylamide gel electrophoresis (PAGE) with subsequent bottom-up identification of peptidic compounds using nano liquid chromatography-tandem mass spectrometry (nanoLC-MS/MS)., Results: Among the 337 substances analyzed in the doping control laboratory in Cologne, 67 active ingredients were found, 49 of which being categorized as doping agents by the World Anti-Doping Agency (WADA). A total of 83.7 % accounted for steroidal substances (predominantly testosterone, trenbolone, and nandrolone and corresponding esters), 12.8 % accounted for peptide hormones and growth factors (predominantly hGH and growth hormone releasing peptides (GHRPs)), 3.2 % of the products contained hormones and metabolic modulators, and 0.3 % accounted for diuretic agents. Outstanding findings were the detection of the selective androgen receptor modulator (SARM) LGD-4033, the thymic hormone thymosin β4, and a fusion protein of unknown biological activity., Conclusions: Trafficking of considerable amounts of arguably performance and/or body-enhancing compounds has been observed during the past 4 years, the majority of which is categorized as relevant to sports drug testing. Several substances are of fake/non-approved nature and represent enormous health risks to the 'customer'.

Rationale: Therapeutic approaches concerning attention-deficit hyperactivity disorder (ADHD) commonly include the administration of drugs amplifying cerebral dopamine and norepinephrine signals. Among these, compounds belonging to the Prohibited List as established by the World Anti-Doping Agency (WADA) are present such as amfetamine or methylphenidate, and abuse of these can result in sanctions for athletes. The recently approved therapeutic lisdexamfetamine represents a slow-release prodrug of amfetamine for ADHD treatment. In order to support doping control laboratories in differentiating the abuse of amfetamine from a therapeutic administration of lisdexamfetamine, the determination of the prodrug from urine is desirable. Since approximately 2% of lisdexamfetamine are eliminated intact into urine, a liquid chromatography/high-resolution/high accuracy mass spectrometric method was developed, allowing the target analyte and one of its metabolites (4-hydroxyamfetamine sulfate) to be accurately quantified., Methods: Urine samples were fortified with fourfold deuterated lisdexamfetamine and analyzed directly using ultrahigh-performance liquid chromatography (UHPLC) interfaced via electrospray ionization to a second-generation quadrupole-orbitrap mass spectrometer. The assay was characterized concerning specificity, limits of quantification (0.15-5 ng/mL), intraday and interday imprecision (4-22%), accuracy (90-120%), linearity, and ion suppression/enhancement effects. A patient's urine samples were analyzed to provide proof-of-principle data demonstrating that the intact prodrug lisdexamfetamine is detectable in urine up to 11 h post-administration at concentrations up to 80 ng/mL. Moreover, amfetamine and sulfoconjugated 4-hydroxyamfetamine were measured, yielding up to 1146 and 56 ng/mL, respectively., Conclusions: Considering the observed comparably low urinary concentrations of lisdexamfetamine and 4-hydroxyamfetamine sulfate, the preferred minimally labor-intense sample preparation, and the necessity of fast and robust result generation, the employed instrumental setup proved fit-for-purpose in sports drug testing., (Copyright © 2014 John Wiley & Sons, Ltd.)

The biogenic amine octopamine [4-(2-amino-1-hydroxyethyl)phenol] is prohibited in sports owing to its stimulating and performance-enhancing properties. Adverse analytical findings in athletes' doping control samples commonly result from surreptitious applications; however, the occurrence of octopamine in nutritional supplements and in selected invertebrates as well as the assumption that its N-methylated analog synephrine [4-(1-hydroxyethyl-2-methylamino)phenol, not banned by anti-doping authorities but currently monitored in prevalence studies) might be converted in-vivo into octopamine have necessitated a study to investigate the elimination of synephrine and octopamine present in over-the-counter products. Urine samples collected after administration of nutritional supplements containing octopamine and/or synephrine as well as urine samples collected after therapeutic application of octopamine- or synephrine-containing drugs were analyzed using a validated solid-phase extraction-based procedure employing a weak cation exchange resin and liquid chromatographic/tandem mass spectrometric detection with electrospray ionization and multiple reaction monitoring. In the case of therapeutic octopamine application, the urinary concentration of the target compound increased from baseline levels below the lower limit of detection to 142 µg/mL, while urine samples collected after synephrine as well as dietary supplement administration did not yield any evidence for elevated renal excretion of octopamine., (Copyright © 2011 John Wiley & Sons, Ltd.)

Manipulation of urine specimens provided by elite athletes for doping control purposes has been reported several times in the past, and in most of these cases urine substitution was eventually proven. Recent findings of suspected and substantiated manipulation have outlined the complexity and diversity of tampering options, sample appearance alterations resulting from non-manipulative influence, and the analytical challenges arising from these scenarios. Using state-of-the-art mass spectrometric and immunological doping control and forensic chemistry methodologies, four unusual findings were observed. One sports drug testing specimen was found to contain an unusually high content of saccharides accompanied by hordenine and Serpine-Z4, while no endogenous steroid (e.g. testosterone, epitestosterone, androsterone and etiocholanolone) was detected. This specimen was identified as non-alcoholic beer filled into the doping control sample container, constituting an undisputed doping offense. A doping control sample of bright green color was received and found to contain residues of methylene blue, which is not considered relevant for doping controls as no masking or manipulative effect is known. In addition, the number of urine samples of raspberry to crimson red coloration received at doping control laboratories has constantly increased during the last years, attributed to the presence of hemoglobin or betanin/isobetanin. Also here, no doping rule violation was given and an impact on routine analytical results was not observed. Finally, a total of 8 sports drug testing samples collected at different competition sites was shown to contain identical urine specimens as indicated by steroid profile analysis and conclusively proven by DNA-STR (short tandem repeat) analysis. Here, the athletes in question were not involved in the urine substitution act but the doping control officer was convicted of sample manipulation., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Benfluorex [1-(m-trifluoromethylphenyl)-2-(β-benzoyloxyethyl)aminopropane] has been widely used for the treatment of atherogenic metabolic disorders and impaired carbohydrate metabolism (particularly in obese type-II diabetic patients) as well as an anorectic drug. Due to its potentially performance-enhancing properties, benfluorex has been added to the list of prohibited compounds and methods of doping by the World Anti-Doping Agency (WADA) in 2010, necessitating the implementation of the drug as well as its major metabolites into routine doping control procedures. In the present study, human urinary metabolites of benfluorex were characterized by gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) as well as liquid chromatography-electrospray ionization-high resolution/high accuracy tandem mass spectrometry (LC-ESI-MS/MS). Commonly employed sports drug testing approaches consisting of liquid-liquid extraction followed by GC-MS or urine dilution and immediate LC-MS/MS analysis were expanded and validated with regard to specificity, recovery (48-54%, GC-MS only), intra- and interday precision (<25%), limits of detection (5-8 ng/mL for LC-MS/MS and 80 ng/mL for GC-MS), and ion suppression (for LC-ESI-MS/MS only) to allow the detection of benfluorex metabolites 1-(m-trifluoromethylphenyl)-2-(2-hydroxyethyl)aminopropane (M1), 1-(m-trifluoromethylphenyl)-2-(2-carboxymethyl)aminopropane (M2), and 1-(m-trifluoromethylphenyl)-2-aminopropane (M3) as well as the glucuronic acid conjugate of M1.

Stimulants have been frequently detected in doping control samples and represent a structurally diverse class of compounds. Comprehensive sports drug-testing procedures have been developed using gas or liquid chromatography combined with mass spectrometric detection, and they have revealed various adverse analytical findings, as demonstrated with 2 examples, 4-methylhexan-2-amine and methoxyphenamine. Moreover, the necessity of controlling the use or misuse of stimulating agents is outlined by means of pseudoephedrine, a compound that was prohibited in sports until the end of 2003. Since the ban was lifted, monitoring programs proved a significant increase in pseudoephedrine applications as determined from urine samples collected in competition. As a consequence, a reimplementation of this drug in future doping controls was decided., (Copyright 2010 Elsevier Inc. All rights reserved.)

New insights into the biochemistry of cardiac arrhythmia and skeletal muscle fatigue have yielded new drug candidates to counteract these phenomena. Major biological targets have become ryanodine receptor (RyR)-based Ca(2+)-release channels, which tend to 'leak' under various circumstances including strenuous exercise and, thus, cause aberrant calcium sparks that entail impaired muscle function. Therapeutics, which are referred to as rycals, are currently being developed to treat cardiac arrhythmia via enhancement of calstabin-ryanodine affinities that causes a stabilization of the RyR. These therapeutics possess potential for misuse in sports, and an early implementation of target analytes such as the benzothiazepine derivatives S-107 and JTV-519 or putative metabolites into doping control screening procedures is recommended. Reference compounds, deuterated analogues, and a putative metabolic product were synthesized, and electron ionization mass spectra of these products were studied and dissociation pathways elucidated by means of tandem mass spectrometry (MS/MS) and accurate mass measurements. The characterized analytes were incorporated into existing sports drug testing assays based on liquid-liquid extraction and subsequent gas chromatography/mass spectrometry (GC/MS) analysis, and specificity, lower limit of detection (4-6 ng/mL), intraday and interday precision (1.5-17.2%), as well as recovery (63-66%) were determined. The established procedure proved suitable for routine doping control analysis to detect a potential misuse of the drug candidate S-107 in elite sport., (Copyright (c) 2009 John Wiley & Sons, Ltd.)

The sympathomimetic agent metamfepramone (2-dimethylamino-1-phenylpropan-1-one, dimethylpropion) is widely used for the treatment of the common cold or hypotonic conditions. Due to its stimulating properties and its rapid metabolism resulting in major degradation products such as methylpseudoephedrine and methcathinone, it has been considered relevant for doping controls by the World Anti-Doping Agency (WADA). The rapid degradation of the active drug complicates the detection of metamfepramone itself but the metabolites methylpseudoephedrine and methcathinone can be monitored, and the finding of the latter in particular allows the inference of a metamfepramone administration. In order to improve sports drug testing procedures, metamfepramone, methylpseudoephedrine and methcathinone were characterized using electrospray ionization-high resolution/high accuracy mass spectrometry, and a method employing liquid chromatography/tandem mass spectrometry was established that allowed the analysis of these three analytes by direct injection of 2 microL of urine specimens. The assay was validated with regard to specificity, lower limits of detection (2-10 ng mL(-1)), intraday and interday precision (3-17%) and ion suppression/enhancement effects. The developed procedure has been used to verify or falsify suspicious signals observed in routine screening procedures based on gas chromatography/mass spectrometry and yielded an adverse analytical finding concerning a metamfepramone administration in an authentic doping control sample. Although the active drug was not detected, the indicative metabolites methylpseudoephedrine and methcathinone were considered sufficient to infer the application of the prohibited drug.

Drug abuse by adolescents has been investigated in various surveys that reported correlations between age, gender, and activity. However, none of these studies included chemical analyses to help substantiate the statements of participants. In the present study, the urine specimens of 964 students (439 females, 525 males; mean age 22.1 years, s = 1.7), who applied to study sports sciences at university, were assessed for anabolic steroids, stimulants, and selected drugs prohibited in sports. In total, 11.2% of the urine specimens provided contained drugs covered by doping controls. The most frequently detected compound was the major metabolite of tetrahydrocannabinol (9.8%) followed by various stimulants related to amphetamine and cocaine (1.0%). Indications of anabolic steroid use were found in 0.4% of urine samples but originated from contraceptives containing norethisterone. The present study provided unambiguous data on the status quo of drug (ab)use by adolescents hoping for a career related to elite sport or sports sciences. No use of anabolic steroids was detected. However, evidence for stimulants and tetrahydrocannabinol administration was obtained, although not reported by any participant, which highlights the issue of under-reporting in surveys based solely on questionnaires.

Methoxyphenamine (o-methoxy-N,alpha-dimethylphenethylamine, Orthoxine) used in earlier times as a bronchodilator is prohibited in sports according to the regulations of the World Anti-Doping Agency (WADA). The drug and several of its metabolites are commonly analysed in doping control screening assays using gas chromatography-mass spectrometry requiring extraction from urine specimens. A complementary method employing liquid chromatography-atmospheric pressure chemical ionisation-tandem mass spectrometry and direct injection of urine aliquots was developed, which provided a fast and sensitive alternative to confirm the presence of the prohibited compound and degradation products in sports drug testing samples. In particular, the chromatographic separation of the active drug from isomeric compounds such as the designer drug p-methoxymetamphetamine (PMMA) was of particular interest to unambiguously identify the applied substance and was accomplished using a C6-phenyl reverse-phase column with isocratic elution. The established procedure was validated for methoxyphenamine with regard to specificity, limit of detection (0.7 ng mL(-1)), intraday- and interday precision (2.5-5.8% and 10.8-16.2%, respectively) and its applicability was demonstrated with an authentic doping control sample which tested positive for the prohibited compound early in 2008.

Stimulatory substances applied during competition possess a reasonable potential as performance enhancing agents and their misuse in elite sport has been frequently reported during the last few decades. An analytical method for the qualitative determination of selected stimulants containing a primary or secondary amine moiety in human urine for doping control purposes was developed. A rapid and highly specific procedure based on a sample preparation using weak cation exchange solid phase extraction (SPE-XCW) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a C6-Phenyl analytical column allowed the unambiguous identification of the target analytes down to low ng mL(-1) concentration levels. Validation provided recovery rates of better than 75%, precisions of less than 20% and a linear approximation in the required working range (10-750 ng mL(-1)) were obtained for 19 different target compounds. This method provides a rugged and highly specific alternative to the established method utilising gas or liquid chromatography after liquid-liquid extraction.

Manipulation of urine sampling in sports drug testing is considered a violation of anti-doping rules and is consequently sanctioned by regulatory authorities. In 2003, three identical urine specimens were provided by three different athletes, and the identity of all urine samples was detected and substantiated using numerous analytical strategies including gas chromatography-mass spectrometry with steroid and metabolite profiling, gas chromatography-nitrogen/phosphorus detector analysis, high-performance liquid chromatography-UV fingerprinting, and DNA-STR (short tandem repeat) analysis. None of the respective athletes was the donor of the urine provided for doping analysis, which proved to be a urine sample collected from other unidentified individual(s). Samples were considered suspicious based on identical steroid profiles, one of the most important parameters for specimen individualization in sports drug testing. A database containing 14,224 urinary steroid profiles of athletes was screened for specific values of 4 characteristic parameters (ratios of testosterone/epitestosterone, androsterone/etiocholanolone, androsterone/testosterone, and 5alpha-androstane-3alpha,17beta-diol/5beta-androstane-3alpha,17beta-diol) and only the three suspicious samples matched all criteria. Further metabolite profiling regarding indicated medications and high-performance liquid chromatography-UV fingerprinting substantiated the assumption of manipulation. DNA-STR analyses unequivocally confirmed that the 3 urine samples were from the same individual and not from the athletes who provided DNA from either buccal cell material or blood specimens. This supportive evidence led to punishment of all three athletes according to the rules of the World Anti-Doping Agency. Application of a new multidisciplinary strategy employing common and new doping control assays enables the detection of urine substitution in sports drug testing.

Since January 2007, the list of prohibited substances established by the World Anti-Doping Agency includes the sympathomimetic compound tuaminoheptane (1-methyl-hexylamine, 2-heptylamine). Primarily used as nasal decongestant drug it has been considered relevant for sports drug testing due to its stimulating properties. A confirmatory gas chromatographic-mass spectrometric procedure was developed including liquid-liquid extraction and imine formation of tuaminoheptane employing various aldehydes and ketones such as formaldehyde, acetaldehyde, benzaldehyde and acetone. Extraction and derivatisation conditions were optimised for utmost efficiency, and characteristic fragment ions obtained after electron ionisation allowed for a sensitive and selective analytical assay, which was validated with regard to recovery (50%), lower limit of detection (20 ng mL(-1)) as well as interday- and intraday precision (<15%). The applicability to authentic urine samples was demonstrated using administration study specimens obtained from two male persons using Rhinofluimucil (tuaminoheptane hemisulfate) for intranasal application. The administered drug was detected up to 46 h after repeated topical instillation of a total of approximately 3 mg.

Since January 2006, the list of prohibited substances established by the World Anti-Doping Agency includes the antidepressant / anti-obesity drug Sibutramine. Due to its rapid degradation to its active metabolites N-desmethyl and N-bisdesmethyl Sibutramine, reference compounds were synthesized and included into an existing screening assay to allow the unambiguous determination of these metabolic products in human urine using liquid-liquid extraction followed by liquid chromatography/tandem mass spectrometry. Characteristic product ions, obtained after electrospray ionization and collision-induced dissociation, were elucidated using high resolution/high accuracy mass measurements with a hybrid linear ion trap/orbitrap mass analyzer. Based on diagnostic product ions, the extended screening procedure was validated for both Sibutramine metabolites using a triple quadrupole mass spectrometer. Items such as lower limits of detection (6-40 ng mL(-1)), recoveries (39-42%), intraday precision (low: 5.5-10.6%, medium: 4.9-5.9%), high: 12.8-16.4%) and interday precision (low: 15.0-22.8%, medium: 17.7-18.6%), high: 16.5-25.6%) were evaluated, and a clinical spot urine sample was analyzed to demonstrate the applicability of the developed assay in sports drug testing.

Massive localized lymphedema is a rare disease. Only a few cases have been described in the literature. These monstrous pseudotumors of the subcutis are mostly localized in the inguinal region or at the lower extremity. These tumors often show a slow growth for many years. Besides hernias, lipomatous tumors must be distinguished. The therapy of choice is the excision of the tumor. Relapse is not uncommon in the few cases described in the literature so far. The diagnostic procedure and therapy of an 48-year-old women with a massive localized lymphedema weighing about 22 kg are demonstrated and discussed.