A mathematical model is presented to simulate the photocatalytic degradation of terbuthylazine in a continuous stirred tank reactor. The flow field is described by the continuity equation and the momentum equation. An advection-diffusion-reaction equation is used to simulate the transport of terbuthylazine.  The chemical reactions take place on the inner wall surface coated with the catalyst, which is described by a third-kind boundary condition.  A transient differential equation is used to describe the variation of inlet concentration with time. All governing equations are solved using the commercial computational fluid software ANSYS Fluent. The simulation results agree with the experimental data at different temperatures and different flow rates. The radial distribution of terbuthylazine in the reactor is discussed in detail. The velocity depicts a parabolic curve with a maximum velocity of  0.0005 m s-1, 0.001 m s-1, 0.00022 m s-1 and 0.0032 m s-1 for 50 mL min-1, 100 mL min-1, 200 mL min-1, and 300 mL min-1, respectively. At the flow rate of 300 mL min-1, concentration of terbuthylazine decreases from 3.6 mg dm-3 to 0.8 mg dm-3 whereas concentration of cyanuric acid increases from 0.05 mg dm-3 to 0.28 mg dm-3. It shows that the radial effect of velocity and concentration should be taken into account. The mathematical model used in this study is suitable for simulating the photocatalytic degradation process of terbuthylazine in continuous stirred tank reactors.

We apply a tracer model linked with a 3D circulation model to simulate transport and fate of water-soluble persistent substances in the Black Sea that do not bioaccumulate to a considerable extent. The model uses specified degradation time and identical concentrations in the rivers to build a correlation between average concentration in the basin and half-life (DT50). The average concentration in certain sub-regions of the Black Sea can be estimated using an exponential dependence of DT50, if DT50 and concentration in rivers are known. Averaging is performed on the simulations from 2000 to 2019 with real atmospheric forcing and river runoff. A well-defined seasonal cycle is evident for the average shelf concentration, while the average concentration in the deep region does not show a pronounced seasonal cycle or inter-annual variations. With the help of the existing observational data, we estimate DT50 and concentration in the rivers for carbamazepine, sulfamethoxazole and terbuthylazine. Atrazine and simazine are believed to have accumulated in the basin for a long time due to their widespread use in the past and the slow rate of degradation in the marine environment.

Semivolatile organic compounds (SVOCs) in air can react with hydroxyl radicals (OH), nitrate radicals (NO₃) and ozone (O₃). Two questions regarding SVOC reactivity with OH, NO₃ and O₃ in the gas and particle phases remain to be addressed: according to the existing measurements in the literature, which are the most reactive SVOCs in air, and how can the SVOC reactivity in the gas and particle phases be predicted? In the present study, a literature review of the second-order rate constant (k) was carried out to determine the SVOC reactivity with OH, NO₃ and O₃ in the gas and particle phases in ambient and indoor air at room temperature. Measured k values were available in the literature for 90 polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphates, dioxins, di(2-ethylhexyl)phthalate (DEHP) and pesticides including pyrifenox, carbamates and terbuthylazine. PAHs and organophosphates were found to be more reactive than dioxins and PCBs. Based on the obtained data, quantitative structure-activity relationship (QSAR) models were developed to predict the k value using quantum chemical, molecular, physical property and environmental descriptors. Eight linear and nonlinear statistical models were employed, including regression models, bagging, random forest and gradient boosting. QSAR models were developed for SVOC/OH reactions in the gas and particle phases and SVOC/O₃ reactions in the particle phase. Models for SVOC/NO₃ and SVOC/O₃ reactions in the gas phase could not be developed due to the lack of measured k values for model training. The least absolute shrinkage and selection operator (LASSO) regression and random forest models were identified as the most effective models for SVOC reactivity prediction according to a comparison of model performance metrics.

Despite intensive ecotoxicological research, we still know relatively little about the ecological impacts of many environmental contaminants. Filling these knowledge gaps is particularly important regarding amphibians, because they play significant roles in freshwater and terrestrial ecosystems, and their populations are declining worldwide. In this study, we investigated two pollutants that have been poorly studied in ecotoxicology despite their widespread occurrence in surface waters: the herbicide terbuthylazine and the pharmaceutical drug carbamazepine. We exposed two anuran species throughout their larval development to each of two environmentally relevant concentrations of each pollutant, and recorded mortality and 17 sub-lethal endpoints up to several months after exposure. Mortality was low and unrelated to treatment. In agile frogs (Rana dalmatina), we found that treatment with 0.3 μg/L terbuthylazine decreased tadpole activity and reduced fat bodies in juveniles, whereas treatment with 50 μg/L carbamazepine decreased spleen size and increased spleen pigmentation. In common toads (Bufo bufo), treatment with 0.003 μg/L terbuthylazine increased body mass at metamorphosis, treatment with 0.3 μg/L terbuthylazine increased the size of optic tecta, and treatment with 0.5 μg/L carbamazepine decreased hypothalamus size. Treatment with 50 μg/L carbamazepine reduced the feeding activity of toad tadpoles, decreased their production of anti-predatory bufadienolide toxins, and increased their body mass at metamorphosis; juvenile toads in this treatment group had reduced spleen pigmentation. Neither treatments affected the time to metamorphosis, post-metamorphic body mass, or sex ratios significantly. These results show that environmental levels of both terbuthylazine and carbamazepine can have several sub-lethal effects on anurans, which may be detrimental to individual fitness and population persistence in natural conditions. Our findings further highlight that toxic effects cannot be generalized between chemicals of similar structure, because the terbuthylazine effects we found do not conform with previously reported effects of atrazine, a related and extensively studied herbicide.

This study examined to what degree bioaccumulated pesticides in transplanted zebra mussels can give an insight to pesticide bioavailability in the environment. In addition, it was investigated if pesticide body residues could be related to ecological responses (changes in macroinvertebrate community composition). For this at 17 locations, 14 pesticide concentrations and nine dissolved metals were measured in translocated zebra mussels and the results were related to the structure of the macroinvertebrate community. Critical body burdens in zebra mussel, above which the ecological status was always low, could be estimated for chlorpyrifos, terbuthylazine and dimethoate being respectively 8.0, 2.08 and 2.0 ng/g dry weight.With multivariate analysis, changes in the community structure of the macroinvertebrates were related to accumulated pesticides and dissolved metals. From this analysis, it was clear that the composition of the macroinvertebrate communities was not only affected by pesticides but also by metal pollution. Two different regions could be clearly separated, one dominated by metal pollution, and one where pesticide pollution was more important.The results of this study demonstrated that zebra mussel body burdens can be used to measure pesticide bioavailability and that pesticide body burdens might give insight in the ecological impacts of pesticide contamination. Given the interrelated impacts of pesticides and heavy metals, it is important to further validate all threshold values before they can be used by regulators.

Pollution by chemical substances is of concern for the maintenance of healthy and sustainable aquatic environments. While the occurrence and fate of numerous emerging contaminants, especially pharmaceuticals, is well documented in freshwater, their occurrence and behavior in coastal and marine waters is much less studied and understood. This study investigates the occurrence of 58 chemicals in the open surface water of the Western Mediterranean Sea for the first time. 70 samples in total were collected in 10 different sampling areas. 3 pesticides, 11 pharmaceuticals and personal care products and 2 artificial sweeteners were detected at sub-ng to ng/L levels. Among them, the herbicide terbuthylazine, the pharmaceuticals caffeine, carbamazepine, naproxen and paracetamol, the antibiotic sulfamethoxazole, the antibacterial triclocarban and the two artificial sweeteners acesulfame and saccharin were detected in all samples. The compound detected at the highest concentration was saccharin (up to 5.23 ng/L). Generally small spatial differences among individual sampling areas point to a diffuse character of sources which are likely dominated by WWTP effluents and runoffs from agricultural areas or even, at least for pharmaceuticals and artificial food additives, from offshore sources such as ferries and cruising ships. The implications of the ubiquitous presence in the open sea of chemicals that are bio-active or toxic at low doses on photosynthetic organisms and/or bacteria (i.e., terbuthylazine, sulfamethoxazole or triclocarban) deserve scientific attention, especially concerning possible subtle impacts from chronic exposure of pelagic microorganisms.

As part of the Endis-Risks project, the current study describes the occurrence of the chlorotriazine pesticides atrazine, simazine and terbutylazine in water, sediment and suspended matter in the Scheldt estuary (B-Nl) from 2002 to 2005 (3 samplings a year, 8 sampling points). Atrazine was found at the highest concentrations, varying from 10 to 736 ng/l in water and from 5 up to 10 ng/g in suspended matter. Simazine and terbutylazine were detected at lower concentrations. Traces of the targeted pesticides were also detected in sediments, but these were below the limit of quantification. As part of an ecotoxicological assessment, we studied the potential effect of atrazine on molting of Neomysis integer (Crustacea:Mysidacea), a resident invertebrate of the Scheldt Estuary and a proposed test organism for the evaluation of endocrine disruption. Following chronic exposure (3 weeks), atrazine did not significantly affect mysid molting at environmentally relevant concentrations (up to 1 μg/l). The water of the Scheldt estuary and its associated suspended solids are contaminated with chlorotriazines at concentrations that do not affect mysid molting.

Terbuthylazine (TBA) has replaced atrazine in many EU countries, becoming one of the most frequently detected pesticides in natural waters. TBA is a compound of emerging concern, due to its persistence, toxicity and proven endocrine disruption activity to wildlife and humans. Techniques applied in water treatment plants remove only partially this herbicide and poor attention is given to the generation and fate of by-products, although some of them have demonstrated an estrogenic activity comparable to atrazine. This paper summarizes the environmental occurrence of TBA and its main metabolite desethylterbuthylazine and reports the performance of an innovative electrochemical cell equipped with a solid polymer electrolyte (SPE) sandwiched between a Ti/RuO₂ cathode and a Boron-Doped Diamond anode, operating at constant current, in the treatment of an aqueous solution of TBA. The herbicide removal in the first 30 min of treatment increases from 42% to 92% as the applied current is increased from 100 to 500 mA. The rate of degradation at 500 mA decreases between 30 and 60 min, with a final abatement of 97%. An 89% removal was reached at 100 mA when the initial TBA concentration was raised from 0.1 to 4 mg L⁻¹ and less than 1% of the herbicide was converted in desethylterbuthylazine and minor metabolites. No chemicals are needed, no sludge is produced. Further research is encouraged, as this technology may be promising for the achievement of a zero-discharge removal of different emerging pollutants as pesticides, pharmaceuticals and personal care products.

Chlorotriazine herbicides (CTs) are widely used pest control chemicals. In contrast to groundwater contamination, little attention has been given to the circumstances of residue formation of parent compounds and transformation products in soils.Seventy-five cultivated floodplain topsoils in the Czech Republic were sampled in early spring of 2015, corresponding to a minimum of six months (current-use terbuthylazine, TBA) and a up to a decade (banned atrazine, AT and simazine, SIM) after the last herbicide application. Soil residues of parent compounds and nine transformation products were quantified via multiple residue analysis using liquid chromatography - tandem mass spectrometry of acetonitrile partitioning extracts (QuEChERS). Using principal component analysis (PCA), their relation to soil chemistry, crops and environmental parameters was determined.Of the parent compounds, only TBA was present in more than one sample. In contrast, at least one CT transformation product, particularly hydroxylated CTs, was detected in 89% of the sites, or 54% for banned triazines. Deethylated and bi-dealkylated SIM or AT residues were not detectable. PCA suggests the formation and/or retention of CT hydroxy-metabolite residues to be related to low soil pH, and a direct relation between TBA and soil organic carbon, and between deethyl-TBA and clay or Ca contents, respectively, the latter pointing towards distinct sorption mechanisms. The low historic application of simazine contrasted by the high abundance of its residues, and the co-occurrence with AT residues suggests the post-ban application of AT and SIM banned triazines as a permitted impurity of TBA formulations as a recent, secondary source.The present data indicate that topsoils do not contain abundant extractable residues of banned parent chlorotriazines, and are thus likely not the current source for related ground- and surface water contamination. In contrast, topsoils might pose a long-term source of TBA and CT transformation products for ground and surface water contamination.

A spatially-explicit version of the recent multimedia fate model SoilPlus was developed and applied to predict the runoff of three pesticides in a small agricultural watershed in north-eastern Italy. In order to evaluate model response to increasing spatial resolution, a tiered simulation approach was adopted, also using a dynamic model for surface water (DynA model), to predict the fate of pesticides in runoff water and sediment, and concentrations in river water. Simulation outputs were compared to water concentrations measured in the basin. Results showed that a high spatial resolution and scenario complexity improved model predictions of metolachlor and terbuthylazine in runoff to an acceptable performance (R2 = 0.64–0.70). The importance was also shown of a field-based database of properties (i.e. soil texture and organic carbon, rainfall and water flow, pesticides half-life in soil) in reducing the distance between predicted and measured surface water concentrations and its relevance for risk assessment.