Lipid-related ion suppression on the herbicide atrazine in earthworm samples in ToF-SIMS and matrix-assisted laser desorption ionization mass spectrometry imaging and the role of gas-phase basicity.

In mass spectrometry imaging (MSI), ion suppression can lead to a misinterpretation of results. Particularly phospholipids, most of which exhibit high gas-phase basicity (GB), are known to suppress the detection of metabolites and drugs. This study was initiated by the observation that the signal of an herbicide, i.e., atrazine, was suppressed in MSI investigations of earthworm tissue sections. Herbicide accumulation in earthworms was investigated by time-of-flight secondary ion mass spectrometry and matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). Additionally, earthworm tissue sections without accumulation of atrazine but with a homogeneous spray deposition of the herbicide were analyzed to highlight region-specific ion suppression. Furthermore, the relationship of signal intensity and GB in binary mixtures of lipids, amino acids, and atrazine was investigated in both MSI techniques. The GB of atrazine was determined experimentally through a linear plot of the obtained intensity ratios of the binary amino acid mixtures, as well as theoretically. The GBs values for atrazine of 896 and 906 kJ/mol in ToF-SIMS and 933 and 987 kJ/mol in MALDI-MSI were determined experimentally and that of 913 kJ/mol by quantum mechanical calculations. Compared with the GB of a major lipid component, phosphatidylcholine (GBPC = 1044.7 kJ/mol), atrazine's experimentally and computationally determined GBs in this work are significantly lower, making it prone to ion suppression in biological samples containing polar lipids.

Mechanistic interpretation of the sorption of terbuthylazine pesticide onto aged microplastics.

Microplastics (MPs) pose a global concern due to their ubiquitous distribution. Once in the environment, they are subject to aging, which changes their chemical-physical properties and ability to interact with organic pollutants, such as pesticides. Therefore, this study investigated the interaction of the hydrophobic herbicide terbuthylazine (TBA), which is widely used in agriculture, with artificially aged polyethylene (PE) MP (PE-MP) to understand how aging affects its sorption. PE was aged by an accelerated weathering process including UV irradiation, hydrogen peroxide, and ultrasonic treatment, and aged particles were characterized in comparison to pristine particles. Sorption kinetics were performed for aged and pristine materials, while further sorption studies with aged PE-MP included determining environmental factors such as pH, temperature, and TBA concentration. Sorption of TBA was found to be significantly lower on aged PE-MP compared to pristine particles because aging led to the formation of oxygen-containing functional groups, resulting in a reduction in hydrophobicity and the formation of negatively charged sites on oxidized surfaces. For pristine PE-MP, sorption kinetics were best described by the pseudo-second-order model, while it was intra-particle diffusion for aged PE-MP as a result of crack and pore formation. Sorption followed a decreasing trend with increasing pH, while it became less favorable at higher temperatures. The isotherm data revealed a complex sorption process on altered, heterogeneous surfaces involving hydrophobic interactions, hydrogen bonding, and π-π interactions, and the process was best described by the Sips adsorption isotherm model. Desorption was found to be low, confirming a strong interaction. However, thermodynamic results imply that increased temperatures, such as those resulting from climate change, could promote the re-release of TBA from aged PE-MP into the environment. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed TBA sorption onto PE.

Isolation of aqueous pesticides on surface-functionalized SBA-15: glyphosate kinetics and detailed empirical insights for atrazine.

Atrazine and glyphosate are two of the most used pesticides around the world causing serious water contamination. In this study, amine-functionalized Santa Barbara Amorphous-15 silica (SBA-15-NH2) was synthesized and employed for the aqueous adsorption of atrazine and glyphosate. The adsorbent was mesoporous post-functionalization with lower surface area, pore volume, size, and stability when compared to the SBA-15. The pesticides adsorption rates were high with over 85% of potential adsorption having occurred within the initial 180 min. The equilibria for atrazine and glyphosate adsorption were 60 and 360 min, respectively, and the rate data fit the fractal pseudo-second-order and pseudo-second-order models, respectively. Atrazine adsorption was higher at lower solution pH with reduced adsorption as the pH value increased. There was enhanced atrazine adsorption as temperature increased from 22 to 32 °C, but further temperature rise resulted in lower adsorption compared to that recorded at 22 °C. The processes comprise electrostatic interaction, trapping of atrazine within mesopores, and multi-layer adsorption of atrazine on surface-adsorbed atrazine. The equilibrium data fitted the Langmuir adsorption isotherm model better than the Freundlich. The SBA-15-NH2 adsorption capacity for atrazine and glyphosate was better than many adsorbents reported in literature, the adsorbent is reusable, and exhibited sustained efficiencies for atrazine that was ≥82% even after 3-cycles, an indication of chemical stability and renewability.

Dose-dependent in vivo effects of formulated moxidectin on seedling emergence of temperate grassland species.

Sheep function as effective endozoochorous seed vectors in grasslands. Recent laboratory-based studies showed that this important function can be impaired by macrocyclic lactone anthelmintics, which are used to control parasites and enter into the environment mainly via faeces; however, there is a lack of in vivo studies. We conducted a seed-feeding experiment with sheep that included four temperate grassland species from four different families (Achillea ptarmica, Asteraceae; Agrostis capillaris, Poaceae; Dianthus deltoides, Caryophyllaceae; Plantago lanceolata, Plantaginaceae). A series of three feeding trials was carried out after one of two groups of sheep received a single administration of a common oral formulation of the macrocyclic lactone moxidectin. Faeces were collected to determine seedling emergence rate and emergence timing as well as moxidectin concentration via HPLC. Seedling emergence differed significantly between the anthelmintic-treated sheep and the control group. This impact depended on time of seed uptake after anthelmintic administration. Number of emerging seedlings was significantly reduced (27.1 %) when faeces moxidectin concentrations were high (on average 3153 ng g-1; 1 d post treatment) and significantly increased (up to 68.8 %) when moxidectin concentrations were low (≤86 ng g-1; 7, 14 d pt). Mean emergence time was significantly lowered at low moxidectin concentrations. These results demonstrate dose-related effects of deworming on seedling emergence which might affect endozoochory and eventually plant population dynamics in grasslands.

Dissent in the sediment? Lake sediments as archives of short- and long-range impact of anthropogenic activities in northeastern Germany.

The suitability of lake sediment cores to reconstruct past inputs, regional pollution, and usage patterns of pesticides has been shown previously. Until now, no such data exist for lakes in eastern Germany. Therefore, 10 sediment cores (length 1 m) of 10 lakes in eastern Germany, the territory of the former German Democratic Republic (GDR), were collected and cut into 5-10-mm layers. In each layer, concentrations of trace elements (TEs) As, Cd, Cr, Cu, Ni, Pb, S, and Zn, as well as of organochlorine pesticides (OCPs), i.e., dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH), were analyzed. A miniaturized solid-liquid extraction technique in conjunction with headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) was used for the latter. The progression of TE concentrations over time is uniform. It follows a trans-regional pattern and is indicative of activity and policy making in West Germany before 1990 instead of those in the GDR. Of OCPs, only transformation products of DDT were found. Congener ratios indicate a mainly aerial input. In the lakes' profiles, several regional features and responses to national policies and measures are visible. Dichlorodiphenyldichloroethane (DDD) concentrations reflect the history of DDT use in the GDR. Lake sediments proved to be suitable to archive short- and long-range impacts of anthropogenic activity. Our data can be used to complement and validate other forms of environmental pollution long-term monitoring and to check for the efficiency of pollution countermeasures in the past.

Single-Locus and Multi-Locus Genome-Wide Association Studies Identify Genes Associated with Liver Cu Concentration in Merinoland Sheep.

Economic losses due to copper intoxication or deficiency is a problem encountered by sheep farmers. The aim of this study was to investigate the ovine genome for genomic regions and candidate genes responsible for variability in liver copper concentration. Liver samples were collected from slaughtered lambs of the Merinoland breed from two farms, and used for measurement of copper concentration and genome-wide association study (GWAS). A total of 45,511 SNPs and 130 samples were finally used for analysis, in which single-locus and several multi-locus GWAS (SL-GWAS; ML-GWAS) methods were employed. Gene enrichment analysis was performed for identified candidate genes to detect gene ontology (GO) terms significantly associated with hepatic copper levels. The SL-GWAS and a minimum of two ML-GWAS identified two and thirteen significant SNPs, respectively. Within genomic regions surrounding identified SNPs, we observed nine promising candidate genes such as DYNC1I2, VPS35, SLC38A9 and CHMP1A. GO terms such as lysosomal membrane, mitochondrial inner membrane and sodium:proton antiporter activity were significantly enriched. Genes involved in these identified GO terms mediate multivesicular body (MVB) fusion with lysosome for degradation and control mitochondrial membrane permeability. This reveals the polygenic status of this trait and candidate genes for further studies on breeding for copper tolerance in sheep.

Validation of a method to determine transformation of chemicals in anaerobic liquid pig and cattle manure for the OECD test guideline programme.

Manure is widely used as a fertilizer and applied to agricultural land. It may contain highly active chemicals like veterinary medicinal products or biocides, which enter into the environment by this pathway. This is recognized by several regulatory frameworks, however, a detailed method for examining the transformation of chemicals in manure was lacking. This article describes the validation of a method for studying the anaerobic transformation of chemicals in pig and cattle liquid manure. Different steps are covered with an emphasis on the validation ring test and the OECD (Organisation for Economic Cooperation and Development) process that led to the recent adoption of the method as OECD Test Guideline (TG) 320.

Adsorption of the hydrophobic organic pollutant hexachlorobenzene to phyllosilicate minerals.

Hexachlorobenzene (HCB), a representative of hydrophobic organic chemicals (HOC), belongs to the group of persistent organic pollutants (POPs) that can have harmful effects on humans and other biota. Sorption processes in soils and sediments largely determine the fate of HCB and the risks arising from the compound in the environment. In this context, especially HOC-organic matter interactions are intensively studied, whereas knowledge of HOC adsorption to mineral phases (e.g., clay minerals) is comparatively limited. In this work, we performed batch adsorption experiments of HCB on a set of twelve phyllosilicate mineral sorbents that comprised several smectites, kaolinite, hectorite, chlorite, vermiculite, and illite. The effect of charge and size of exchangeable cations on HCB adsorption was studied using the source clay montmorillonite STx-1b after treatment with nine types of alkali (M+: Li, K, Na, Rb, Cs) and alkaline earth metal cations (M2+: Mg, Ca, Sr, Ba). Molecular modeling simulations based on density functional theory (DFT) calculations to reveal the effect of different cations on the adsorption energy in a selected HCB-clay mineral system accompanied this study. Results for HCB adsorption to minerals showed a large variation of solid-liquid adsorption constants Kd over four orders of magnitude (log Kd 0.9-3.3). Experiments with cation-modified montmorillonite resulted in increasing HCB adsorption with decreasing hydrated radii of exchangeable cations (log Kd 1.3-3.8 for M+ and 1.3-1.4 for M2+). DFT calculations predicted (gas phase) adsorption energies (- 76 to - 24 kJ mol-1 for M+ and - 96 to - 71 kJ mol-1 for M2+) showing a good correlation with Kd values for M2+-modified montmorillonite, whereas a discrepancy was observed for M+-modified montmorillonite. Supported by further calculations, this indicated that the solvent effect plays a relevant role in the adsorption process. Our results provide insight into the influence of minerals on HOC adsorption using HCB as an example and support the relevance of minerals for the environmental fate of HOCs such as for long-term source/sink phenomena in soils and sediments.

Temperature moderates impact of formulated moxidectin on seed germination of three temperate grassland species.

Formulations of macrocyclic lactone anthelmintics such as moxidectin are regularly administered to sheep to combat parasites. A disadvantage of these pharmaceuticals are their side effects on non-target organisms when entering the environment. Little is known about anthelmintic effects on plant reproduction and whether the effects depend on environmental factors. For ecological and methodological reasons, we aimed at testing whether temperature affects the efficacy of a common moxidectin-based formulation on seed germination. We carried out a germination experiment including three typical species of temperate European grasslands (Centaurea jacea, Galium mollugo, Plantago lanceolata). We applied three temperature regimes (15/5, 20/10, 30/20°C), and a four-level dilution series (1:100-1:800) of formulated moxidectin (i.e., Cydectin oral drench). These solutions represent seed-anthelmintic contacts in the digestive tract of sheep shortly after deworming. In addition, a control was carried out with purified water only. We regularly counted emerging seedlings and calculated final germination percentage, mean germination time and synchrony of germination. Formulated moxidectin significantly reduced percentage, speed and synchrony of germination. A 1:100 dilution of the formulation reduced germination percentage by a quarter and increased mean germination time by six days compared to the control. Temperature moderated effects of the anthelmintic drug on germination in all response variables and all species, but in different patterns and magnitudes (significant anthelmintic x temperature x species interactions). In all response variables, the two more extreme temperature regimes (15/5, 30/20°C) led to the strongest effects of formulated moxidectin. With respect to germination percentage, G. mollugo was more sensitive to formulated moxidectin at the warmest temperature regime, whereas P. lanceolata showed the highest sensitivity at the coldest regime. This study shows that it is important to consider temperature dependencies of the effects of pharmaceuticals on seed germination when conducting standardised germination experiments.

Toxicogenomic differentiation of functional responses to fipronil and imidacloprid in Daphnia magna.

Active substances of pesticides, biocides or pharmaceuticals can induce adverse side effects in the aquatic ecosystem, necessitating environmental hazard and risk assessment prior to substance registration. The freshwater crustacean Daphnia magna is a model organism for acute and chronic toxicity assessment representing aquatic invertebrates. However, standardized tests involving daphnia are restricted to the endpoints immobility and reproduction and thus provide only limited insights into the underlying modes-of-action. Here, we applied transcriptome profiling to a modified D. magna Acute Immobilization test to analyze and compare gene expression profiles induced by the GABA-gated chloride channel blocker fipronil and the nicotinic acetylcholine receptor (nAChR) agonist imidacloprid. Daphnids were expose to two low effect concentrations of each substance followed by RNA sequencing and functional classification of affected gene ontologies and pathways. For both insecticides, we observed a concentration-dependent increase in the number of differentially expressed genes, whose expression changes were highly significantly positively correlated when comparing both test concentrations. These gene expression fingerprints showed virtually no overlap between the test substances and they related well to previous data of diazepam and carbaryl, two substances targeting similar molecular key events. While, based on our results, fipronil predominantly interfered with molecular functions involved in ATPase-coupled transmembrane transport and transcription regulation, imidacloprid primarily affected oxidase and oxidoreductase activity. These findings provide evidence that systems biology approaches can be utilized to identify and differentiate modes-of-action of chemical stressors in D. magna as an invertebrate aquatic non-target organism. The mechanistic knowledge extracted from such data will in future contribute to the development of Adverse Outcome Pathways (AOPs) for read-across and prediction of population effects.

Sorption of selected antiparasitics in soils and sediments.

BACKGROUND: Veterinary pharmaceuticals can enter the environment when excreted after application and burden terrestrial and aquatic ecosystems. However, knowledge about the basic process of sorption in soils and sediments is limited, complicating regulatory decisions. Therefore, batch equilibrium studies were conducted for the widely used antiparasitics abamectin, doramectin, ivermectin, and moxidectin to add to the assessment of their environmental fate. RESULTS: We examined 20 soil samples and six sediments from Germany and Morocco. Analysis was based on HPLC-fluorescence detection after derivatization. For soils, this resulted in distribution coefficients K D of 38-642 mL/g for abamectin, doramectin, and ivermectin. Moxidectin displayed K D between 166 and 3123 mL/g. Normalized to soil organic carbon, log K OC coefficients were 3.63, 3.93, 4.12, and 4.74 mL/g, respectively, revealing high affinity to organic matter of soils and sediments. Within sediments, distribution resulted in higher log K OC of 4.03, 4.13, 4.61, and 4.97 mL/g for the four substances. This emphasizes the diverse nature of organic matter in both environmental media. The results also confirm a newly reported log KOW for ivermectin which is higher than longstanding assumptions. Linear sorption models facilitate comparison with other studies and help establish universal distribution coefficients for the environmental risk assessment of veterinary antiparasitics. CONCLUSIONS: Since environmental exposure affects soils and sediments, future sorption studies should aim to include both matrices to review these essential pharmaceuticals and mitigate environmental risks from their use. The addition of soils and sediments from the African continent (Morocco) touches upon possible broader applications of ivermectin for human use. Especially for ivermectin and moxidectin, strong sorption further indicates high hydrophobicity and provides initial concern for potential aquatic or terrestrial ecotoxicological effects such as bioaccumulation. Our derived K OW estimates also urge to re-assess this important regulatory parameter with contemporary techniques for all four substances. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1186/s12302-021-00513-y.

Exposure to DDT and HCH congeners and associated potential health risks through khat (Catha edulis) consumption among adults in South Wollo, Ethiopia.

Khat (Catha edulis) chewing is widespread in the region of East Africa. Even low levels of organochlorine pesticides (OCPs) in khat could induce public health concern. In a market-based study, from five popular khat varieties, a total of 35 composite khat samples were analyzed for dichlorodiphenyltrichloroethane (DDT) and its main transformation products, and four hexachlorocyclohexane (HCH) isomers. Extraction was carried out by quick, easy, cheap, effective, rugged and safe method (QuEChERS). OCP concentrations were determined by head space solid phase microextraction coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS). Every sample contained ß-HCH above the maximum residue limit set by the European Commission. For total DDT, this was the case for 25.7% of the samples. The ratios of (p,p'-DDD + p,p'-DDE) to p,p'-DDT were less than one for 85% of khat samples, demonstrating recent use of DDT in khat farmlands. Conversely, the ratio of ß-HCH to total HCH varied from 0.56 to 0.96, implying historical input of technical HCH. Assuming a daily chewable portion of 100 g, dietary intakes of p,p'-DDT, total DDT and total HCH by adults ranged from 3.12 to 57.9, 6.49 to 80.2 and 39.2 to 51.9 ng (kg body weight)-1 day-1, respectively. These levels are below acceptable levels suggested by international organizations. Chewing khat showed lower non-cancer health risk, but showed relatively higher cancer risk in terms of OCPs. Because khat is chewed without being subjected to any treatment, uncertainties associated with estimated intakes and health risks should be low. Therefore, this practice is of great concern.

Honeybee colonies compensate for pesticide-induced effects on royal jelly composition and brood survival with increased brood production.

Sublethal doses of pesticides affect individual honeybees, but colony-level effects are less well understood and it is unclear how the two levels integrate. We studied the effect of the neonicotinoid pesticide clothianidin at field realistic concentrations on small colonies. We found that exposure to clothianidin affected worker jelly production of individual workers and created a strong dose-dependent increase in mortality of individual larvae, but strikingly the population size of capped brood remained stable. Thus, hives exhibited short-term resilience. Using a demographic matrix model, we found that the basis of resilience in dosed colonies was a substantive increase in brood initiation rate to compensate for increased brood mortality. However, computer simulation of full size colonies revealed that the increase in brood initiation led to severe reductions in colony reproduction (swarming) and long-term survival. This experiment reveals social regulatory mechanisms on colony-level that enable honeybees to partly compensate for effects on individual level.

Utilizing eco-friendly kaolinite-biochar composite adsorbent for removal of ivermectin in aqueous media.

Several emerging contaminants are currently used in an unregulated manner worldwide, resulting in their increasing stringent limits in water by regulatory bodies. Thus, more viable and cheap treatment technologies are required. Recently, synergistic combinations of low-cost adsorbents have shown huge potential for aqueous toxic metals adsorption in water treatment processes. However, there is dearth of data on their potential for emerging contaminant removal. Here, low-cost kaolinite (KAC) clay was synergistically combined with blended Carica papaya or pine cone seeds, and calcined to obtain composites of KAC-Carica papaya seeds (KPA) and KAC-pine cone seeds (KPC). These adsorbents were characterized and evaluated for ivermectin adsorption at varying operating times (15-1440 min), pH (3-11), concentration (100-600 µg/L), and temperature (19.5-39.5 °C), as well as testing adsorbents' reusability. The composites exhibited marked property differences including over 250% cation exchange capacity increases and ≥50% surface area decreases, but unchanged KAC clay primary lattice structure. Ivermectin adsorption data were explained using kinetics and adsorption isotherm models. The rate of adsorption on KAC decreased over time, while rates for KPA and KPC increased until equilibrium at 180 min; the presence of biomaterials in the composites conferred better ivermectin adsorption and retention under continuous agitation. The adsorbents exhibited dual adsorption peaks one each at the acidic and alkaline pH regions as solution pH changed from 3 to 11. The rate data fitted (≥0.9232) the homogeneous fractal Pseudo-Second Order (FPSO) better than any other kinetics model, as well as the Freundlich adsorption isotherm model (≥0.9887); these indicate complex interactions between ivermectin and the adsorption sites of both composites. Ambient temperature increase up to ≈30 °C caused higher ivermectin adsorption but beyond this temperature there was drastic drop in adsorption. The KPA and KPC adsorption capacities are 105.3 and 115.8 µg/g, respectively. The KPC was better at reducing ivermecitn in low-concentration solution (≈75 µg/L) to less than 5.0 µg/L compared with KPA with ≈20.0 µg/L. Though KPC showed better efficiency in adsorption capacity and lowering concentration in low-concentration solutions, KPA exhibited better reusability with 83.5 and 67.5% initial adsorption strengths remaining in the second and third adsorption cycles, respectively, compared to the 73.8 and 58.8% for the KPC. These results indicate that KPA and KPC composites have the economic potential for application in water treatment processes.

Detection of artificial sweeteners and iodinated X-ray contrast media in wastewater via LC-MS/MS and their potential use as anthropogenic tracers in flowing waters.

The detection of wastewater impact on stream chemistry is often hindered by high background concentrations of ubiquitous solutes. In the present study we tested the applicability of artificial sweeteners (AS) and iodinated X-ray contrast media (ICM) as tracers to detect this impact by examining wastewater treatment plant (WWTP) effluents and surface water samples. The developed direct injection LC-MS/MS method enabled the detection of these anthropogenic micropollutants in aqueous samples down to trace level concentrations. The 2-h-composite sampling of WWTP effluent revealed fluctuating ICM concentrations between and within days with highest concentrations at the end of the week. Diatrizoic acid (DTZ) and iopromide (IOP) were the predominant ICM with concentrations up to 7 µg/L. Concentrations of the AS acesulfame (ACE) fluctuated between 0.5 µg/L and 1 µg/L. Concentrations of AS and ICM in surface water were both associated with wastewater impact. DTZ contamination was more widespread whereas some sampling points exhibited a more pronounced contamination with non-ionic ICM. Surface water was frequently contaminated with AS. Particularly ACE was detected in every surface water sample indicating that it is chemically stable and that inputs to the aquatic environment via WWTP effluents are widespread. The broad application of ACE as food additive enables its application as a tracer throughout Germany. Furthermore, the developed LC-MS/MS method enables rapid detection of ACE down to the low ng/L-range. Nonetheless, DTZ or IOP could be used in addition to ACE to verify anthropogenic influences on natural waters.

Eprinomectin from a sustained release formulation adversely affected dung breeding insects.

The insecticidal activity of parasiticide residues in dung of cattle treated with a sustained release eprinomectin formulation was examined, and an improved eprinomectin dung residue extraction method is presented. Emergent insect abundance and richness were significantly reduced in all post-treatment intervals (7, 14, 28, 56, 84, 112, and 140 d), relative to pre-treatment. Emergent insect diversity was reduced for between 84 and 112 d post-treatment. Collembola were not affected by residues. Chemical analyses subsequently documented residues of eprinomectin in dung of each collection period post-treatment at levels expected based on previously reported excretion profiles for this product. Cattle subcutaneously injected with this product excreted residues that reduced dung-breeding insect emergence for 5 mo post-treatment. The consequences of these long-term non-target effects to pasture ecosystems are not known.

Proper experimental design requires randomization/balancing of molecular ecology experiments.

Properly designed (randomized and/or balanced) experiments are standard in ecological research. Molecular methods are increasingly used in ecology, but studies generally do not report the detailed design of sample processing in the laboratory. This may strongly influence the interpretability of results if the laboratory procedures do not account for the confounding effects of unexpected laboratory events. We demonstrate this with a simple experiment where unexpected differences in laboratory processing of samples would have biased results if randomization in DNA extraction and PCR steps do not provide safeguards. We emphasize the need for proper experimental design and reporting of the laboratory phase of molecular ecology research to ensure the reliability and interpretability of results.

Similar but not the same: metal concentrations in hair of three ecologically similar, forest-dwelling bat species (Myotis bechsteinii, Myotis nattereri, and Plecotus auritus).

Recently, a number of studies demonstrated the suitability of hair analysis to assess metal exposure of bats. As many bat species are endangered, such a non-destructive method is particularly suited for this taxon. The present study analyzed the levels of two non-essential (cadmium and lead) and four essential metals (copper, manganese, molybdenum, and zinc) in hairs of three ecologically similar, sympatric bat species, Bechstein's bat (Myotis bechsteinii), Natterer's bat (Myotis nattereri), and Brown long-eared bat (Plecotus auritus) from an area in Central Hesse (Germany), as well as metal concentrations in soil samples from the bats' foraging habitats. Applying a previously established protocol, the analyses were performed using microwave-assisted extraction followed by inductively coupled plasma optical emission spectrometry. Cadmium and lead concentrations in hair did not differ significantly among the three studied species, whereas the following significant differences existed for levels of essential metals in hair. Manganese concentrations in hair were higher in M. bechsteinii and P. auritus than in M. nattereri and Cu concentrations were higher in M. nattereri than in P. auritus. Myotis bechsteinii showed higher Zn concentrations compared to P. auritus and lower Mo concentrations compared to M. nattereri. Reasons for the observed differences among the three studied species could be differential exposure to these metal elements in their foraging areas, related to variation in the species composition of their arthropod diet in combination with different metal levels in the respective prey species, and/or species-specific requirements for essential metals and related variation in physiological regulation of these elements in the bats.

Can solid-phase microextraction replace solvent extraction for water analysis in fish bioconcentration studies with highly hydrophobic organic chemicals?

With the aim to refine water analysis in fish bioconcentration studies, automated solid-phase microextraction (SPME) was used as an alternative approach to conventional solvent extraction (liquid-liquid extraction [LLE]) for the extraction of 3 hydrophobic organic chemicals (HOCs; log KOW 5.5-7.8) from flow-through studies with rainbow trout (Oncorhynchus mykiss). The results showed that total concentrations extracted by SPME combined with internal standards and LLE are equal. The results further verify the possibility of simultaneous extraction of total and freely dissolved HOC concentrations by SPME. Freely dissolved concentrations allow the assessment of sorption and bioavailability of HOCs in bioconcentration studies and their potential impact on resulting bioconcentration factors (BCFs). Reduction in freely dissolved water concentrations can result in an underestimation of BCFs if they are calculated based on total water concentrations. For polychlorinated biphenyl (PCB) 153, a significant increase in BCF value was observed when freely dissolved concentrations were taken into account. However, log BCF values calculated based on freely dissolved concentrations did not correlate linearly with log KOW values above 5 to 6. This pointed to further influences besides a reduction in freely dissolved water concentrations by sorption to organic matter. The results can aid in assessment of the factors that influence bioconcentration systems and also give important information regarding the possible replacement of LLE by SPME for water analysis of highly HOCs in fish bioconcentration studies. Environ Toxicol Chem 2017;36:2887-2894. © 2017 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.

Adsorptive removal of 2,4,6-trichlorophenol in aqueous solution using calcined kaolinite-biomass composites.

Synergistically combined low-cost composites may be effective for the potential treatment of effluents containing organic pollutants. Hence, preparation of Carica-papaya-modified-kaolinite (CPK) and pine-cone-modified-kaolinite (PCK) composites via calcination of pure kaolinite (KAC), Carica-papaya and pine-cone seeds is demonstrated. The composites' specific surface areas were reduced by more than 57% but no structural modification in KAC lattice d-spacing, indicating impregnation of calcined biomass on clay surfaces and pores. However, composites' cation exchange capacities were enhanced over 4-fold, indicating higher potential for adsorption. Adsorption of 2,4,6-trichlorophenol on composites and KAC showed that CPK and PCK attained equilibrium relatively faster (30 min) compared to KAC (60 min). Modeling studies showed that 2,4,6-trichlorophenol removal mechanisms involved electrostatic interactions on sites of similar energy. Modification enhanced adsorption by 52 and 250% in PCK and CPK, respectively, and adsorption increased with temperature.