The effect of polystyrene microplastic and biosolid application on the toxicity and bioaccumulation of cadmium for Enchytraeus crypticus.

Plastics smaller than 5 mm that end up in a soil environment are known as microplastics (MPs). Microplastics have become a common contaminant in agricultural areas in addition to metals. However, the effect of cadmium (Cd) on soil organisms has not been clearly defined in the presence of MPs. In addition to MPs, biosolid application as a soil amendment in agricultural lands is also leading to shifts in soil conditions, such as the concentrations of nutrients and organic matter. Therefore, the aim of this study is to investigate the toxicity and bioaccumulation of Cd for Enchytraeus crypticus in the presence of polystyrene (PS)-MPs and biosolids to provide insight into their possible interactions. The lethal toxic concentration (LC50) for Cd was higher than 650 mg Cd/kg dry soil for all conditions. The presence of PS-MPs increased the toxicity of Cd for which EC50 was 102 and 38 mg Cd/kg dry soil without and with Cd, respectively, which may be the result of an increased exposure rate through adsorption of Cd on PS-MPs. On the contrary, the presence of biosolids decreased the toxicity of Cd where EC50 was 193 and 473 mg Cd/kg dry soil for the sets applied with 0.6 and 0.9 g biosolids, respectively. Coexistence of biosolids and PS-MPs decreased the reproduction toxicity of Cd, which is similar to the biosolid effect (EC50 is 305 mg Cd/kg dry soil). Bioaccumulation of Cd only positively correlated with its initial concentration in soil and was not affected by the presence of PS-MPs or biosolids. Integr Environ Assess Manag 2023;19:489-500. © 2022 SETAC.

Insights into the acute effect of anti-inflammatory drugs on activated sludge systems with high solids retention time.

The increase in the occurrence of the pharmaceuticals in the environmental compartments is becoming emerging concern as it reflects their inefficient treatment in the wastewater treatment plants which are the main sources of these micropollutants. Non-steroidal anti-inflammatory drugs (NSAIDs) are one of the most commonly prescribed and frequently detected pain medications in wastewater treatment plants. A lab scale sequencing batch reactor (SBR) was operated for seven months and acute inhibitory effect of NSAIDs on activated sludge was tested with respirometry. Culture amendment with different concentrations of NSAIDs in the presence as well as absence of nitrification inhibitor resulted in considerable variation in the oxygen uptake rate (OUR) profiles. The decrease in OUR and nitrate production rate governed with reduced heterotrophic and nitrification activity. The kinetics of half saturation for growth and maximum autotrophic growth rates are determined to be affected negatively by the acute impact of anti-inflammatory pharmaceuticals even at the environmentally relevant concentrations. High removal of tested NSAIDs was observed even for the first time introduce with these compounds.

Effect of triclosan and its photolysis products on marine bacterium V. fischeri and freshwater alga R. subcapitata.

The use of antibacterial agents in consumer products may lead to adverse effects in waters receiving treated wastewater. Triclosan is one of the antibacterial agents used widely in the world and its high usage leads to relatively high concentrations in wastewater effluents. In this study, the probable effect of triclosan in receiving waters was assessed using different organisms. The EC50 values were 668 ±â€¯80 µg/L and 7.8 ±â€¯0.1 µg/L, for Vibrio fischeri and Raphidocelis subcapitata, respectively, indicating the higher sensitivity of the alga. The toxicity of triclosan upon exposure to UV light decreased for both species, as suggested by the increase in EC50 values (1300 ±â€¯50 µg/L and 8.7 ±â€¯0.6 µg/L for V. fischeri and R. subcapitata, respectively). The effect of photolysis on toxicity reduction was higher for V. fischeri and the EC50 values were similar for direct and indirect photolysis. LC-MS/MS analysis of samples with and without UV exposure suggested a decrease in triclosan concentration as well as formation of photolysis byproducts upon photolysis.

The effect of soil properties on the toxicity and bioaccumulation of Ag nanoparticles and Ag ions in Enchytraeus crypticus.

Standard natural Lufa soils (2.2, 2.3 and 5M) with different organic carbon contents (0.67-1.61%) and pHCaCl2 (5.5-7.3) were spiked with ionic Ag (AgNO3) and polyvinyl pyrrolidone (AgNP-PVP) and citrate (AgNP-Cit) coated Ag nanoparticles (NPs). Enchytraeus crypticus were exposed for 21 days to assess effects on survival and reproduction. Soil, pore water and animals were analyzed for Ag. AgNP-Cit had a strong increasing effect on soil pH, leading to high enchytraeid mortality at concentrations higher than 60-100mg Ag/kg dry soil which made it impossible to determine the influence of soil properties on its toxicity. LC50s were lower for AgNO3 than for AgNP-PVP (92-112 and 335-425mg Ag/kg dry soil, respectively) and were not affected by soil properties. AgNO3 and AgNP-PVP had comparable reproductive toxicity with EC50s of 26.9-75.2 and 28.2-92.3mg Ag/kg dry soil, respectively; toxicity linearly increased with decreasing organic carbon content of the soils but did not show a clear effect of soil pH. Ag uptake in the enchytraeids was higher at higher organic carbon content, but could not explain differences in toxicity between soils. This study indicates that the bioavailability of both ionic and nanoparticulate Ag is mainly affected by soil organic carbon, with little effect of soil pH.

An approach for environmental risk assessment of engineered nanomaterials using Analytical Hierarchy Process (AHP) and fuzzy inference rules.

The usage of Engineered Nanoparticles (ENPs) in consumer products is relatively new and there is a need to conduct environmental risk assessment (ERA) to evaluate their impacts on the environment. However, alternative approaches are required for ERA of ENPs because of the huge gap in data and knowledge compared to conventional pollutants and their unique properties that make it difficult to apply existing approaches. This study aims to propose an ERA approach for ENPs by integrating Analytical Hierarchy Process (AHP) and fuzzy inference models which provide a systematic evaluation of risk factors and reducing uncertainty about the data and information, respectively. Risk is assumed to be the combination of occurrence likelihood, exposure potential and toxic effects in the environment. A hierarchy was established to evaluate the sub factors of these components. Evaluation was made with fuzzy numbers to reduce uncertainty and incorporate the expert judgements. Overall score of each component was combined with fuzzy inference rules by using expert judgements. Proposed approach reports the risk class and its membership degree such as Minor (0.7). Therefore, results are precise and helpful to determine the risk management strategies. Moreover, priority weights calculated by comparing the risk factors based on their importance for the risk enable users to understand which factor is effective on the risk. Proposed approach was applied for Ag (two nanoparticles with different coating) and TiO2 nanoparticles for different case studies. Results verified the proposed benefits of the approach.

Agglomeration of Ag and TiO2 nanoparticles in surface and wastewater: Role of calcium ions and of organic carbon fractions.

This study aims to investigate factors leading to agglomeration of citrate coated silver (AgNP-Cit), polyvinylpyrrolidone coated AgNPPVP and titanium dioxide (TiO2) nanoparticles in surface waters and wastewater. ENPs (1 mg/L) were spiked to unfiltered, filtered, ultrafiltered (<10 kDa and <1 kDa) samples. Z-average particle sizes were measured after 1 h, 1 day and 1 week. AgNP-PVP was stable in all fractions of the samples and kept their original size around 60 nm over 1 week. Agglomeration of AgNP-Cit and TiO2 was positively correlated with Ca(2+) concentration, but dissolved organic carbon concentrations > 2 mg/L contributed to stabilizing these NP. Moreover, agglomeration of AgNP-Cit in the various organic matter fractions showed that high molecular weight organic compounds such as biopolymers provide stabilization in natural water. A generalized scheme for the agglomeration behavior of AgNP-Cit, AgNP-PVP and TiO2 in natural waters was proposed based on their relation with Ca(2+), Mg(2+) and DOC concentration.

Toxicokinetics and toxicodynamics of differently coated silver nanoparticles and silver nitrate in Enchytraeus crypticus upon aqueous exposure in an inert sand medium.

The aim of the present study was to evaluate the effect of silver nanoparticles (AgNPs) on Enchytraeus crypticus, applying a combined toxicokinetics and toxicodynamics approach to understand the relationship between survival and the development of internal Ag concentrations in the animals over time. Toxicity tests were conducted in medium composed of well-defined aqueous solutions added to inert quartz sand to avoid the complexity of soil conditions. Citrate-coated AgNPs (AgNP-Cit) and polyvinylpyrrolidone-coated AgNPs (AgNP-PVP) were tested and compared with silver nitrate (AgNO3), which was used as a positive control for Ag ion effects. The median lethal concentration (LC50) values based on Ag concentrations in the solution phase of the test medium decreased over time and reached steady state after 7 d, with AgNO3 and AgNP-PVP being more toxic than AgNP-Cit. Slow dissolution may explain the low uptake kinetics and lower toxicity of AgNP-Cit compared with the other 2 Ag forms. The LC50 values based on internal Ag concentrations in the animals were almost stable over time, highlighting the importance of integrating toxicokinetics and toxicodynamics and relating survival with internal Ag concentrations. Neither survival-based elimination rates nor internal LC50s in the organisms showed any significant evidence of nano-specific effects for both AgNPs, although they suggested some uptake of particulate Ag for AgNP-Cit. The authors conclude that the toxicity of both types of AgNP probably is mainly attributable to the release of Ag ions.

Acute and chronic responses of denitrifying culture to diclofenac.

Acute and chronic effect as well as biodegradation potential at different sludge retention times (SRTs) of a priority pollutant, diclofenac on denitrification process was assessed. The continuous amendment of the culture for 6months with 1µg/L diclofenac resulted in 30% decrease in gas production. The average diclofenac removal observed in the diclofenac-acclimated culture was less than 15%. Batch tests showed that nitrate was removed in diclofenac free-control reactor at a higher rate compared to diclofenac amended reactor. Although, SRT did not have any progressive effect on diclofenac degradation, the system operated at low SRT was more sensitive to diclofenac and resulted in an increase in N2O emission. Wastewater treatment plants (WWTPs) operated at higher SRTs may tolerate and recover from the adverse effects of such micropollutants. The study can lead to other researchers to understand the fate and effect of other emerging pollutants in the anoxic unit of WWTPs.

A systematic evaluation of agglomeration of Ag and TiO2 nanoparticles under freshwater relevant conditions.

This study aims to investigate effects of freshwater components in order to predict agglomeration behavior of silver nanoparticles coated with citrate (AgNP-Cit), polyvinylpyrrolidone (AgNP-PVP), and of TiO2 nanoparticles. Agglomeration studies were conducted in various media based on combinations of ions, natural organic matter (humic, fulvic acid) and surfactants (sodium dodecyl sulfate, alkyl ethoxylate), at a constant ionic strength of 10 mM over time for up to 1 week. Agglomeration level of AgNP-Cit and TiO2 was mostly dependent on the concentration of Ca(2+) in media, and their size strongly increased to micrometer scale over 1 week. However, AgNP-Cit and TiO2 were stabilized to particle size around 500 nm in the presence of NOM, surfactants and carbonate over 1 week. AgNP-PVP maintained their original size in all media except in the presence of Mg(2+) ions which led to significant agglomeration. Behavior of these engineered nanoparticles was similar in a natural freshwater medium.

Optimization of diclofenac quantification from wastewater treatment plant sludge by ultrasonication assisted extraction.

A rapid quantification method of diclofenac from sludge samples through ultrasonication assisted extraction and solid phase extraction (SPE) was developed and used for the quantification of diclofenac concentrations in sludge samples with liquid chromatography/tandem mass spectrometry (LC-MS/MS). Although the concentration of diclofenac in sludge samples taken from different units of wastewater treatment plants in Istanbul was below the limit of quantification (LOQ; 5ng/g), an optimized method for sludge samples along with the total mass balances in a wastewater treatment plant can be used to determine the phase with which diclofenac is mostly associated. Hence, the results will provide information on fate and transport of diclofenac, as well as on the necessity of alternative removal processes. In addition, since the optimization procedure is provided in detail, it is possible for other researchers to use this procedure as a starting point for the determination of other emerging pollutants in wastewater sludge samples.

Seasonal variation of diclofenac concentration and its relation with wastewater characteristics at two municipal wastewater treatment plants in Turkey.

The pharmaceutically active compound diclofenac has been monitored during one year at separate treatment units of two municipal wastewater treatment plants (WWTPs) to evaluate its seasonal variation and the removal efficiency. Conventional wastewater characterization was also performed to assess the possible relationship between conventional parameters and diclofenac. Diclofenac concentrations in the influent and effluent of both WWTPs were detected in the range of 295-1376 and 119-1012ng/L, respectively. Results indicated that the higher diclofenac removal efficiency was observed in summer season in both WWTPs. Although a consistency in diclofenac removal was observed in WWTP_1, significant fluctuation was observed at WWTP_2 based on seasonal evaluation. The main removal mechanism of diclofenac in the WWTPs was most often biological (55%), followed by UV disinfection (27%). When diclofenac removal was evaluated in terms of the treatment units in WWTPs, a significant increase was achieved at the treatment plant including UV disinfection unit. Based on the statistical analysis, higher correlation was observed between diclofenac and suspended solids concentrations among conventional parameters in the influent whereas the removal of diclofenac was highly correlated with nitrogen removal efficiency.

Occurrence of THM and NDMA precursors in a watershed: Effect of seasons and anthropogenic pollution.

In pristine watersheds, natural organic matter is the main source of disinfection by-product (DBP) precursors. However, the presence of point or non-point pollution sources in watersheds may lead to increased levels of DBP precursors which in turn form DBPs in the drinking water treatment plant upon chlorination or chloramination. In this study, water samples were collected from a lake used to obtain drinking water for Istanbul as well as its tributaries to investigate the presence of the precursors of two disinfection by-products, trihalomethanes (THM) and N-nitrosodimethylamine (NDMA). In addition, the effect of seasons and the possible relationships between these precursors and water quality parameters were evaluated. The concentrations of THM and NDMA precursors measured as total THM formation potential (TTHMFP) and NDMA formation potential (NDMAFP) ranged between 126 and 1523µg/L THM and <2 and 1648ng/L NDMA, respectively. Such wide ranges imply that some of the tributaries are affected by anthropogenic pollution sources, which is also supported by high DOC, Cl(-) and NH(3) concentrations. No significant correlation was found between the water quality parameters and DBP formation potential, except for a weak correlation between NDMAFP and DOC concentrations. The effect of the sampling location was more pronounced than the seasonal variation due to anthropogenic pollution in some tributaries and no significant correlation was obtained between the seasons and water quality parameters.