A kinetic study of the photolysis of sulfamethoxazole with special emphasis on the photoisomer.

The previously not studied photochemical degradation of sulfamethoxazole (SMX) to the isomer of SMX (ISO) was measured via a polychromatic (Xe) and a monochromatic (Hg) light source and accompanied by quantum chemical DFT calculations. In addition to the [Formula: see text] of ISO, tautomer-dependent properties such as the [Formula: see text] were measured and theoretically confirmed by DFT. The kinetics in solutions below and above the [Formula: see text] of SMX were studied for the available and quantifiable products SMX, ISO, 3-amino-5-methylisoxazole (AMI), 2-amino-5-methyloxazole (AMO), and sulfanilic acid (SUA). The quantum yields of the neutral ([Formula: see text]) and anionic [Formula: see text]) forms of SMX ([Formula: see text], [Formula: see text]) and ISO ([Formula: see text] and [Formula: see text]) were found to be wavelength-independent. In a competitive reaction to the formation of ISO from SMX, the degradation product TP271 is formed. Various proposed structures for TP271 described in the literature have been studied quantum mechanically and can be excluded for thermodynamic reasons. In real samples in a northern German surface water in summer 2021 mean concentrations of SMX were found in the range of 120 ng/L. In agreement with the pH-dependent yields, concentrations of ISO were low in the range of 8 ng/L.

Quantum chemical calculation of the vapor pressure of volatile and semi volatile organic compounds.

The vapor pressure is a specific and temperature-dependent parameter that describes the volatility of a substance and thus its driving force for evaporation or sublimation into the gas phase. Depending on the magnitude of the vapor pressure, there are different methods for experimental determination. However, these are usually associated with a corresponding amount of effort and become less accurate as the vapor pressure decreases. For purposes of vapor pressure prediction, algorithms were developed that are usually based on quantitative structure-activity relationships (QSAR). The quantum mechanical (QM) approach followed here applies an alternative, much less empirical strategy, where the change in Gibbs free energy for the transition from the condensed to the gas phase is obtained from conformer ensembles computed for each phase separately. The results of this automatic, so-called CRENSO workflow are compared with experimentally determined vapor pressures for a large set of environmentally relevant compounds. In addition, comparisons are made with the single structure-based COSMO-RS QM approach, linear-free-energy relationships (LFER) as well as results from the SPARC program. We show that our CRENSO workflow is superior to conventional prediction models and provides reliable vapor pressures for liquids and sub-cooled liquids over a wide pressure range.

Quantum Chemical Calculation and Evaluation of Partition Coefficients for Classical and Emerging Environmentally Relevant Organic Compounds.

Octanol/water (KOW), octanol/air (KOA), and hexadecane/air (KHdA) partition coefficients are calculated for 67 organic compounds of environmental concern using computational chemistry. The extended CRENSO workflow applied here includes the calculation of extensive conformer ensembles with semiempirical methods and refinement through density functional theory, taking into account solvation models, especially COSMO-RS, and thermostatistical contributions. This approach is particularly advantageous for describing large and nonrigid molecules. With regard to KOW and KHdA, one can refer to many experimental data from direct and indirect measurement methods, and very good matches with results from our quantum chemical workflow are evident. In the case of the KOA values, however, good matches are only obtained for the experimentally determined values. Larger systematic deviations between data computed here and available, nonexperimental quantitative structure-activity relationship literature data occur in particular for phthalic acid esters and organophosphate esters. From a critical analysis of the coefficients calculated in this work and comparison with available literature data, we conclude that the presented quantum chemical composite approach is the most powerful so far for calculating reliable partition coefficients because all physical contributions to the conformational free energy are considered and the structure ensembles for the two phases are generated independently and consistently.

Sensory Perception of Non-Deuterated and Deuterated Organic Compounds.

The chemical background of olfactory perception has been subject of intensive research, but no available model can fully explain the sense of smell. There are also inconsistent results on the role of the isotopology of molecules. In experiments with human subjects it was found that the isotope effect is weak with acetone and D6 -acetone. In contrast, clear differences were observed in the perception of octanoic acid and D15 -octanoic acid. Furthermore, a trained sniffer dog was initially able to distinguish between these isotopologues of octanoic acid. In chromatographic measurements, the respective deuterated molecule showed weaker interaction with a non-polar liquid phase. Quantum chemical calculations give evidence that deuterated octanoic acid binds more strongly to a model receptor than non-deuterated. In contrast, the binding of the non-deuterated molecule is stronger with acetone. The isotope effect is calculated in the framework of statistical mechanics. It results from a complicated interplay between various thermostatistical contributions to the non-covalent free binding energies and it turns out to be very molecule-specific. The vibrational terms including non-classical zero-point energies play about the same role as rotational/translational contributions and are larger than bond length effects for the differential isotope perception of odor for which general rules cannot be derived.

Temporal dynamics and ecotoxicological risk assessment of personal care products, phthalate ester plasticizers, and organophosphorus flame retardants in water from Lake Victoria, Uganda.

For the first time the occurrence of 25 organic micropollutants (OMPs) including; 11 personal care products (PCPs), six phthalate ester plasticizers (PEPs) and eight organophosphorus flame retardants (OPFRs) was investigated in 72 water samples obtained from five bays in the Uganda sector of Lake Victoria. In addition, an assessment of the potential ecotoxic risk of the target OMPs to aquatic organisms was conducted. Water samples were analyzed for the target OMPs using gas chromatography coupled with mass spectrometry (GC/MS). All the target PCPs were found in all the water samples with the exception of musk ketone and 2,6-di-tert-butylphenol. Triclosan (89-1400 ng L-1), benzophenone (36-1300 ng L-1), and 4-methylbenzylidine camphor (21-1500 ng L-1) were the most predominant PCPs. All the six plasticizers were found in all the water samples with dibutyl phthalate (350-16 000 ng L-1), and bis-(2-ethylhexyl) phthalate (210-23 000 ng L-1) detected at the highest concentrations. Five OPFRs out of the eight targeted were found in all the water samples. Tricresyl phosphate (25-8100 ng L-1), tris-(2-chloroethyl) phosphate (24-6500 ng L-1) and triphenyl phosphate (54-4300 ng L-1) were the most dominant OPFRs. The highest concentrations of OMPs were recorded in Murchison and Thurston Bays, presumably due to industrial wastewater effluents from the highly industrialized localities of the two Bays. Ecotoxicological risk assessment showed that PCPs (triclosan, musk ketone, and 4-MBC), plasticizers (dibutyl phthalate, bis-(2-ethylhexyl) adipate and bis-(2-ethylhexyl) phthalate) and OPFRs (tricresyl phosphate, triphenyl phosphate and tris-(2-chloroethyl) phosphate) pose a high ecotoxic risk to lives of aquatic organisms (risk quotients, RQ > 1).

Natural clay as a sorbent to remove pharmaceutical micropollutants from wastewater.

Worldwide, the aquatic environment is contaminated by micro-pollutants, such as ingredients of personal care products, pesticides and pharmaceuticals. This contamination is one of the major environmental issues of global concern. Adsorption is one of approach, which has been most extensively discussed within recent years for the reduction of the input of micro-pollutants into the environment. In the present study, the natural clay classified as Na-montmorillonite, was characterized and tested for its potential to remove four model compounds representing different polarity and ionizability: i) diatrizoic acid (DAT), ii) iopamidol (IOP), iii) metformin (MTF), and iv) carbamazepine (CBZ). The adsorption efficiency of clay was evaluated by initial compound concentration, effect of pH, contact time and temperature. The results indicated that clay was able to remove the pharmaceuticals from aqueous medium with an efficiency of 70% for CBZ and MTF. In contrast, clay showed a lower removal of 30% for DAT and no removal for IOP. The results indicate that clay could rapidly and efficiently reduce the concentration of CBZ and MTF, which could provide a solution to remove some substances, without undesirable by-product generation. However, this study clearly demonstrated that removal rates strongly depend on the compound. Albeit chemical structure may play a role for the different degree of removal, this study could not completely explain the sorption mechanism between sorbent-sorbate interactions.

Occurrence, distribution, and ecotoxicological risk assessment of selected pharmaceutical compounds in water from Lake Victoria, Uganda.

The occurrence of 24 pharmaceuticals (including 15 antibiotics, three analgesic/anti-inflammatory drugs, three anti-epileptic/antidepressant drugs, two beta blockers, and one lipid regulator) was investigated in 75 water samples collected from four bays in the Ugandan part of Lake Victoria. In addition, the potential environmental risk of the target pharmaceutical compounds to aquatic organisms in the aquatic ecosystem of Lake Victoria was assessed. Water samples were extracted using solid phase extraction and analyzed for pharmaceuticals using high-performance liquid chromatography coupled with triple quadrupole mass spectrometry (LC/MS/MS). Eighteen of the 24 pharmaceuticals occurred at quantifiable concentrations. Sulfamethoxazole (1-5600 ng L-1), trimethoprim (1-89 ng L-1), tetracycline (3-70 ng L-1), sulfacetamide (1-13 ng L-1), and ibuprofen (6-780 ng L-1) occurred at quantifiable concentrations in all water samples. Sulfamethazine (2-50 ng L-1), erythromycin (10-66 ng L-1), diclofenac (2-160 ng L-1), and carbamazepine (5-72 ng L-1) were only quantifiable in water samples from Murchison Bay. The highest concentrations of pharmaceuticals were found in Murchison Bay, the main recipient of sewage effluents, industrial and municipal waste from Kampala city via the Nakivubo channel. Ecotoxicological risk assessment showed that sulfamethoxazole, oxytetracycline, erythromycin, and diclofenac pose a high toxic risk to aquatic organisms in the lake, while ciprofloxacin, norfloxacin, and ibuprofen pose a medium risk. This study is the first of its kind to report the levels and ecotoxic risks of pharmaceutical compounds in Lake Victoria waters, of Uganda, and East Africa as a whole.

Photochemistry of 9-acridinecarboxaldehyde in aqueous media.

Dark and photolysis reactions in solution were investigated for 9-acridinecarboxaldehyde (ACL). ACL reacts in the dark at T = 20 °C and pH = 7.0 in an air saturated solution to the main product 9-acridinecarboxylic acid (ACA) and to the minor product 9-acridinemethanol (ACM) with a lifetime of τ = 4.3 days. The dissociation constant of the base ACLH+ was determined to be pKa ± σ = 4.38 ± 0.04. The photolysis of ACL was investigated using a polychromatic Xe-light source. The quantum yield in aqueous solution at T = 20 °C in a concentration range of c0(ACL) = 0.18-16.6 µM for pH > pKa and for nitrogen, air and oxygen aerated solutions was found to be Φ ± σ = (0.015 ± 0.003) mol/mol, independent from concentration. The quantum yield of ACLH+, i.e. for pH ≪ pKa, is by a factor of 2 higher (Φ = 0.029 mol/mol). Quantum yields in methanol and isopropanol are slightly lower compared to water and in acetone lower by about a factor of 20. In acetonitrile ACL was found to be practically photostable. Minimum lifetimes in sunlight for a measurement on September 5, 2017 were in the range of τ = 5-10 minutes. The diurnal photolysis of ACL in sunlight was satisfactory explained using the mean quantum yield, the absorption spectrum and photon fluxes with suitable corrections for cloudiness and the dimensions of the setup. For low concentrations ACR is formed with a yield of practically 100% in the photolysis reaction. However, with increasing concentration of ACL yields of ACR decrease and yields of ACA increase. 9(10H)-Acridinone and ACM were always detected as minor products with yields below 2%. 9-Methylacridine was never detected in any reaction of ACL. Strong indications are presented of a photolysis reaction of ACL in a river located in Lower Saxony (Germany) with a corresponding equimolar formation of ACR. ACL is therefore a direct precursor of ACR in natural surface water.

Sources of nitrogen heterocyclic PAHs (N-HETs) along a riverine course.

For the first time the occurrence of 26 nitrogen heterocyclic polyaromatic hydrocarbons (N-HETs) and the antiepileptic drug carbamazepine (CBZ) as a marker for anthropogenic influence was determined in an entire river system and its influents. Besides the investigation of diurnal and annual variations in concentrations, dilution and load calculations, the aims were to facilitate transferability to other rivers by identifying sources of the different substances. To create a sufficient database over 180 aqueous samples from the River Fuhse (Lower Saxony, Germany), its catchment area, effluents of municipal and industrial wastewater treatment plants (WWTPs) and rainwater were analyzed. Typical substances found in background water samples and rain samples were quinoline and isoquinoline, whereas 1-/3-methylisoquinoline were traced back to an industrial WWTP. Due to similar concentration levels in the effluents of municipal WWTPs, their impact on the river correlated with their nominal loads. In municipal WWTP effluents CBZ (cmedian=1693ngL-1), 2-methylquinoline (cmedian=64ngL-1), and acridine (cmedian=62ngL-1) prevailed. Although the occurrence of N-HETs at contaminated sites is a widely discussed scientific topic, this study showed that the investigated site was a source with only small volumetric contribution to N-HET concentrations in the adjacent river. In total the River Fuhse discharges 20kga-1 N-HETs and 21kga-1 CBZ into the receiving river.

Development and application of a simultaneous SPE-method for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, heterocyclic PAHs (NSO-HET) and phenols in aqueous samples from German Rivers and the North Sea.

Polycyclic aromatic hydrocarbons (PAHs), heterocyclic PAHs (NSO-HETs), alkylated PAHs and phenols are known as the prevailing contaminants in groundwater at tar contaminated sites. Besides these local sources, the concentrations and the distribution in particular of NSO-HETs in environmental samples, such as rivers, have received notably less attention. To investigate their occurrence in river basins two sensitive analytical methods for the simultaneous extraction of 86 substances including NSO-HETs, classical EPA-PAHs, alkylated PAHs and phenols were developed: liquid-liquid extraction for the whole water phase and solid phase extraction for the dissolved water phase only. Solely GC-MS or additionally LC-MSMS for fractionated basic nitrogen heterocycles (N-HETs) were used for quantification. Limits of quantification were in the low ngL(-1) range. Concentrations were determined in 29 aqueous samples from 8 relatively large rivers located in Lower Saxony (Germany) and the North Sea. NSO-HETs had comparable or even higher sum concentrations than EPA-PAHs. N-HETs, especially acridine and quinolines with concentrations of up to 20ngL(-1) per substance, were predominant.

In situ air-water and particle-water partitioning of perfluorocarboxylic acids, perfluorosulfonic acids and perfluorooctyl sulfonamide at a wastewater treatment plant.

In situ measurements of air and water phases at a wastewater treatment plant (WWTP) were used to investigate the partitioning behavior of perfluorocarboxylic acids (PFCAs), perfluorosulfonic acids (PFSAs) and perfluorooctyl sulfonamide (HFOSA) and their conjugate bases (PFC(-)s, PFS(-)s, and FOSA(-), respectively). Particle-dissolved (Rd) and air-water (QAW) concentration ratios were determined at different tanks of a WWTP. Sum of concentrations of C4-12,14 PFC(A)s, C4,6,8,10 PFS(A)s and (H)FOSA were as high as 50 pg m(-3) (atmospheric gas phase), 2300 ng L(-1) (aqueous dissolved phase) and 2500 ng L(-1) (aqueous particle phase). Particle-dissolved concentration ratios of total species, log Rd, ranged from -2.9 to 1.3 for PFS(A)s, from -1.9 to 1.1 for PFC(A)s and was 0.71 for (H)FOSA. These field-based values agree well with equilibrium partitioning data reported in the literature, suggesting that any in situ generation from precursors, if they are present in this system, occurs at a slower rate than the rate of approach to equilibrium. Acid QAW were also estimated. Good agreement between the QAW and the air-water equilibrium partition coefficient for C8PFCA suggests that the air above the WWTP tanks is at or near equilibrium with the water. Uncertainties in these QAW values are attributed mainly to variability in pKa values reported in the literature. The WWTP provides a unique environment for investigating environmental fate processes of the PFCAs and PFSAs under 'real' conditions in order to better understand and predict their fate in the environment.

Plant traits affecting herbivory on tree recruits in highly diverse subtropical forests.

Differences in herbivory among woody species can greatly affect the functioning of forest ecosystems, particularly in species-rich (sub)tropical regions. However, the relative importance of the different plant traits which determine herbivore damage remains unclear. Defence traits can have strong effects on herbivory, but rarely studied geographical range characteristics could complement these effects through evolutionary associations with herbivores. Herein, we use a large number of morphological, chemical, phylogenetic and biogeographical characteristics to analyse interspecific differences in herbivory on tree saplings in subtropical China. Unexpectedly, we found no significant effects of chemical defence traits. Rather, herbivory was related to the plants' leaf morphology, local abundance and climatic niche characteristics, which together explained 70% of the interspecific variation in herbivory in phylogenetic regression. Our study indicates that besides defence traits and apparency to herbivores, previously neglected measures of large-scale geographical host distribution are important factors influencing local herbivory patterns among plant species.

Inside-sediment partitioning of PAH, PCB and organochlorine compounds and inferences on sampling and normalization methods.

Comparability of sediment analyses for semivolatile organic substances is still low. Neither screening of the sediments nor organic-carbon based normalization is sufficient to obtain comparable results. We are showing the interdependency of grain-size effects with inside-sediment organic-matter distribution for PAH, PCB and organochlorine compounds. Surface sediment samples collected by Van-Veen grab were sieved and analyzed for 16 PAH, 6 PCB and 18 organochlorine pesticides (OCP) as well as organic-matter content. Since bulk concentrations are influenced by grain-size effects themselves, we used a novel normalization method based on the sum of concentrations in the separate grain-size fractions of the sediments. By calculating relative normalized concentrations, it was possible to clearly show underlying mechanisms throughout a heterogeneous set of samples. Furthermore, we were able to show that, for comparability, screening at < 125 µm is best suited and can be further improved by additional organic-carbon normalization.