Understanding Interface Exchanges for Assessing Environmental Sorption of Additives from Microplastics: Current Knowledge and Perspectives.

Although the impacts of plastic pollution have long been recognized, the presence, pervasiveness, and ecotoxicological consequences of microplastic-i.e., plastic particles < 5 mm-contamination have only been explored over the last decade. Far less focus has been attributed to the role of these materials and, particularly, microplastics, as vectors for a multitude of chemicals, including those (un)intentionally added to plastic products, but also organic pollutants already present in the environment. Owing to the ubiquitous presence of microplastics in all environmental matrices and to the diverse nature of their chemical and physical characteristics, thoroughly understanding the mechanistic uptake/release of these compounds is inherently complex, but necessary in order to better assess the potential impacts of both microplastics and associated chemicals on the environment. Herein, we delve into the known processes and factors affecting these mechanisms. We center the discussion on microplastics and discuss some of the most prominent ecological implications of the sorption of this multitude of chemicals. Moreover, the key limitations of the currently available literature are described and a prospective outlook for the future research on the topic is presented.

A Complete Guide to Extraction Methods of Microplastics from Complex Environmental Matrices.

Sustainable development is a big global challenge for the 21st century. In recent years, a class of emerging contaminants known as microplastics (MPs) has been identified as a significant pollutant with the potential to harm ecosystems. These small plastic particles have been found in every compartment of the planet, with aquatic habitats serving as the ultimate sink. The challenge to extract MPs from different environmental matrices is a tangible and imperative issue. One of the primary specialties of research in environmental chemistry is the development of simple, rapid, low-cost, sensitive, and selective analytical methods for the extraction and identification of MPs in the environment. The present review describes the developments in MP extraction methods from complex environmental matrices. All existing methodologies (new, old, and proof-of-concept) are discussed and evaluated for their potential usefulness to extract MPs from various biotic and abiotic matrices for the sake of progress and innovation. This study concludes by addressing the current challenges and outlining future research objectives aimed at combating MP pollution. Additionally, a set of recommendations is provided to assist researchers in selecting appropriate analytical techniques for obtaining accurate results. To facilitate this process, a proposed roadmap for MP extraction is presented, considering the specific environmental compartments under investigation. By following this roadmap, researchers can enhance their understanding of MP pollution and contribute to effective mitigation strategies.

'Green' coagulant application with activated carbon: dosing sequence and removal of selected micropollutants and effluent organic matter from municipal wastewater.

Combination of 'green' coagulation and powdered activated carbon adsorption was tested for removal of benzophenone (BP), benzophenone-3 (BP-3) and caffeine (CF) from treated municipal wastewater at realistic concentration levels (1-2 µg/L). At the same time it was tracked how the process affected effluent organic matter (EfOM) by measuring chemical oxygen demand (COD). Green coagulant was produced from dry common bean seed in laboratory. Combined coagulation-adsorption experiments were performed by applying different dosing sequences of process materials. Removal of hydrophobic BP and BP-3 by separate adsorption (from 79 to 98%) was not significantly hindered by the addition of the coagulant (activated carbon dose of 5 or 20 mg/L). However, in some cases negative effects were observed for hydrophilic caffeine, depending on the carbon dose, dosing sequence and presence of total suspended solids (TSS). Thus, when coagulant was firstly added into water without TSS before low activated carbon dose of 5 mg/L, caffeine removal dropped from 26% to 5%. Conversely, when TSS were present in the water sample, the removal of caffeine was not hindered under the same PAC dose and dosing sequence. The importance of the process optimisation related to removal of organic micropollutans of different hydrophilicity has been shown in this paper. Removal of around 30% of COD regardless of the dosing sequence was achieved.

Repurposing spent filter sand from iron and manganese removal systems as an adsorbent for treating arsenic contaminated drinking water.

Waterworks which utilise river bank filtration water sources often have to apply aeration and sand filtration to remove iron and manganese during the drinking water treatment process. After some time, the sand becomes saturated and the spent filter sand (SFS) must be disposed of and replaced. In order to valorize this waste stream, this paper investigates the reuse of SFS as an adsorbent for the treatment of arsenic contaminated drinking water. The arsenic removal performance of SFS is compared with two synthetic iron oxide coated sands (IOCS). The sorbents were first characterized by SEM, EDS, BET specific surface area, and point of zero charge (pHpzc) measurements, and then investigated under a variety of conditions. The surface of the SFS was revealed to be coated with iron manganese binary oxide. The Freundlich model best described the isotherm experiment data, indicating a non monolayer adsorption model for arsenic adsorption on the three IOCS investigated. As(III) and As(V) removals were negatively effected by the presence of PO43- and HA anions as they competed with the arsenic species for adsorption sites. However, given the status of SFS as a waste material, the results obtained in this paper suggest it may be successfully reused as a very economically and environmentally sustainable solution for small waterworks requiring both As(V) and As(III) removal during drinking water treatment.

Implications of COVID-19 pandemic on environmental compartments: Is plastic pollution a major issue?

The COVID-19 anthropause has impacted human activities and behaviour, resulting in substantial environmental and ecological changes. It has assisted in restoring the ecological systems by improving, for instance, air and water quality and decreasing the anthropogenic pressure on wildlife and natural environments. Notwithstanding, such improvements recessed back, even to a greater extent, when considering increased medical waste, hazardous disinfectants and other chemical compounds, and plastic waste disposal or mismanagement. This work critically reviews the short- and long-term implications of measures against COVID-19 spreading, namely on human activities and different environmental compartments. Furthermore, this paper highlights strategies towards environmental restoration, as the recovery of the lost environment during COVID-19 lockdown suggests that the environmental degradation caused by humans can be reversible. Thus, we can no longer delay concerted international actions to address biodiversity, sustainable development, and health emergencies to ensure environmental resilience and equitable recovery.

Understanding plastic degradation and microplastic formation in the environment: A review.

Plastic waste are introduced into the environment inevitably and their exposure in the environment causes deterioration in mechanical and physicochemical properties and leads to the formation of plastic fragments, which are considered as microplastics when their size is < 5 mm. In recent years, microplastic pollution has been reported in all kinds of environments worldwide and is considered a potential threat to the health of ecosystems and humans. However, knowledge on the environmental degradation of plastics and the formation of microplastics is still limited. In this review, potential hotspots for the accumulation of plastic waste were identified, major mechanisms and characterization methods of plastic degradation were summarized, and studies on the environmental degradation of plastics were evaluated. Future research works should further identify the key environmental parameters and properties of plastics affecting the degradation in order to predict the fate of plastics in different environments and facilitate the development of technologies for reducing plastic pollution. Formation and degradation of microplastics, including nanoplastics, should receive more research attention to assess their fate and ecological risks in the environment more comprehensively.

Adsorption mechanisms of chlorobenzenes and trifluralin on primary polyethylene microplastics in the aquatic environment.

Microplastics are ubiquitous in aqueous media, and the importance of considering their impact on the behaviour of other compounds in water has often been highlighted. This work thus investigates the adsorption mechanism of six priority substances (as defined by European Union legislation: trichlorobenzenes (1,2,3-TeCB, 1,3,5-TeCB, 1,2,4-TeCB), pentachlorobenzene (PeCB), hexachlorobenzene (HeCB), and trifluralin (TFL)) on primary polyethylene (PE) microplastics (polyethylene standard and polyethylene microparticles isolated from two personal care products) in Danube river water and a synthetic matrix. The maximum adsorbed amounts of the compounds investigated on PEs ranged from 227 µg/g for 1,2,3-TeCB to 333 µg/g for TFL. Equilibrium data was analysed using five isotherm models, with the best fit being described by the Langmuir model and the Dubinin-Radushkevich model indicating chemisorption as the likely sorption mechanism. In general, the Langmuir model showed that the investigated compounds will be better adsorbed on PEs in real river water, with the exception of 1,3,5-TeCB on all studied PEs, where the model predicts better sorption in the synthetic matrix. Compound characteristics and the polymer properties were the most important factors affecting the sorption process, while a significant matrix effect was also observed on PE behaviour. The fact that polyethylene particles derived from personal care products showed greater adsorption capacities than virgin PE demonstrates the necessity of investigating real-world PE samples when assessing the potential impact of MPs in the environment.

Synthesis, characterization and application of magnetic nanoparticles modified with Fe-Mn binary oxide for enhanced removal of As(III) and As(V).

Arsenic contamination of drinking water sources is a widespread global problem. Of the As species commonly found in groundwater, As(III) is generally more mobile and toxic than As(V). In this work, magnetic nanoparticles (MNp) modified with Fe-Mn binary oxide (MNp-FeMn) were synthesized in order to develop a low cost adsorbent with high removal efficiency for both arsenic species which can be readily separated from water using a magnetic field. MNp-FeMn were characterized using different techniques including SEM/EDS, XRD and BET analysis. Adsorption of As(III) and As(V) on MNp-FeMn was studied as a function of initial arsenic concentration, contact time, pH, and coexisting anions. The BET specific surface area of MNp-FeMn was 109 m2/g and maghemite (γ-Fe2O3) was the dominant precipitated phase. The adsorption rate of As(III) and As(V) on MNp-FeMn was controlled by surface diffusion. FTIR analysis confirms that surface complexation through ligand exchange was the main mechanism for As(III) and As(V) removal on MNp-FeMn, with As(III) conversion to As(V) occurring on the adsorbent surface. The maximal adsorption capacity qmax of MNp for As(III) (26 mg/g) was significantly improved after modification with Fe-Mn binary oxide (56 mg/g), while qmax for As(V) was 51 and 54 mg/g, respectively. PO43-, SiO32- and CO32- reduced As(III) and As(V) uptake at higher concentrations. MNp-FeMn can be easily regenerated and reused with only a slight reduction in adsorption capacity. The high oxidation and sorption capacity of MNp-FeMn, magnetic properties and reusability, suggest this material is a highly promising adsorbent for treatment of arsenic contaminated groundwater.

Fate of natural organic matter and oxidation/disinfection by-products formation at a full-scale drinking water treatment plant.

This paper investigates the fate of natural organic matter (NOM) during the full-scale drinking water treatment plant supplied by Danube river bank filtration. After the recent reconstruction of the plant, special attention was devoted to the effects of ozone dose and granulated activated carbon (GAC) filtration on the formation and behaviour of oxidation by-products (carbonyl compounds and bromate), as well as carbonaceous and nitrogenous chlorination by-products. For the oxidation of aromatic NOM moieties that absorb light at UV254, a lower ozone dose (1.0 g O3/m3) is sufficient, whereas to achieve a measurable reduction (about 20%) of total organic carbon, an ozone dose of 1.5 g O3/m3 is required. The content of carbonyl compounds in the water after ozonation increases relative to the content before oxidation treatment, and is up to 12 times higher in the case of aldehydes and up to 2 times higher in the case of carboxylic acids. Seasonal variations, including changes in temperature and the amount of precipitation, were also shown to affect the content of organic matter in the raw water, with slight effects on the quality of the treated water. In the winter, the organic matter content is slightly higher, meaning their transformation products aldehydes and carboxylic acids, are also higher during the winter than the summer.

Removal of selected emerging micropollutants from wastewater treatment plant effluent by advanced non-oxidative treatment - A lab-scale case study from Serbia.

The presence of 48 emerging micropollutants was tested in influent and effluent from primary and secondary treatment at a municipal wastewater treatment plant (WWTP) in Serbia. Sixteen emerging micropollutants (active pharmaceutical ingredients, bisphenols, parabens and UV filters) had concentrations >LOQ (max. conc. 33.4 µg/L). The removal efficiency of primary treatment ranged from 2.0% - 96.0%. In the case of secondary treatment, except for ketoprofen (61.0%), diclofenac (62.6%) and carbamazepine (-20.0%), all other measured micropollutants had removal efficiency above 77.0%. Advanced non-oxidative lab-scale treatments were investigated. Powdered activated carbon (PAC) adsorption achieved removal efficiencies in the range 52.4-99.9%, novel coagulation with natural coagulant isolated from beans achieved removal efficiencies in range 3.2-99.9%, conventional coagulation with ferric chloride 3.12-96.4%, combined adsorption/coagulation 2.69-99.9% and combined PAC/ultrafiltration (PAC/UF) 60-99.9%. For most of the micropollutants, their removal efficiencies were similar to that reported in the literature. Novel natural coagulant showed significant potential compared to the conventional coagulant during a short episode of sub-optimal WWTP operation. When natural coagulant was applied as a part of an adsorption/coagulation hybrid process, there was no negative effect on PAC adsorption, while for conventional coagulant that was not always the case. Also, a structure property relationship (SPR) study revealed correlations between the removal efficiency of the majority of treatments applied and total polar surface area (TPSA) of the micropollutants.

Application of UV-activated persulfate and peroxymonosulfate processes for the degradation of 1,2,3-trichlorobenzene in different water matrices.

The presence of a large number of micropollutants in the environment, including priority and emerging substances, poses a significant risk to surface and groundwater quality. Among them, trichlorobenzenes are widely used in the syntheses of dyes, pesticides, solvents, and other chemicals and have been identified as priority pollutants by the European Water Framework Directive. The main goal of this study was to investigate the behavior of 1,2,3-trichlorobenzene (TCB) during the sulfate radical-based advanced oxidation processes (SR-AOPs) involving UV activation of persulfate or peroxymonosulfate (UV/S2O82- and UV/HSO5- processes). For this purpose, TCB was subjected to SR-AOPs in synthetic water matrices containing humic acids or hydrogencarbonate and natural water samples and a comparative evaluation of the degradation process was made. The toxicity of the oxidation by-products was also assessed. The evaluation of TCB degradation kinetics results using principal component analysis indicates that the efficacy of the SR-AOPs was highly dependent on the pH, initial oxidant concentration, UV fluence, and matrix characteristics. In natural waters, TCB degradation by the UV/S2O82- process proved to be most effective in acidic conditions (pH 5), while the UV/HSO5- process showed the highest efficacy in basic conditions (pH 9.5), achieving a maximum TCB degradations of 97-99%. The obtained results indicate that UV/S2O82- and UV/HSO5- as new generation oxidation processes have significant potential for TCB removal from water and result in only minor toxicity after treatment (14-23% of Vibrio fischeri bioluminescence inhibition).

Investigation of chlorinated phenols sorption mechanisms on different layers of the Danube alluvial sediment.

The characteristics of the Danube river alluvial sediment are of great importance in assessing the risk for transport of pollutants to drinking water sources. Characterization of the sediment column layers has shown that the alluvial sediment, sampled near the city of Novi Sad, is a mesoporous sandy material with certain differences in the properties of individual layers. In order to investigate the sorption mechanisms of four chlorinated phenols (CPs) on the alluvial deposit, static sorption experiments were performed at pH 4, 7 and 10. The results of sorption experiments, confirmed by principal components analysis sugest different mechanisms govern the sorption process at different pH conditions. This can be attributed to the molecular characteristics of CPs, geosorbent properties and to variations in the surface charge of the sorbent at different pH conditions.

Kinetics, mechanism and toxicity of intermediates of solar light induced photocatalytic degradation of pindolol: Experimental and computational modeling approach.

In this work, we have investigated the stability of pindolol (PIN), a non-selective ß1-blocker detected in the river and wastewater of hospitals, in water solution under solar irradiation. Further, detailed insights into the stability of PIN were obtained by the density functional theory (DFT) calculations and molecular dynamics simulations. The kinetics of PIN photocatalytic degradation and mineralization has been studied using four commercial photocatalysts ZnO and TiO2 (P25, Hombikat, and Wackherr). It was found that the major role in degradation of PIN play the reactive hydroxyl radicals. The structures of degradation intermediates were suggested by LC-ESI-MS/MS and DFT calculations. Also, DFT calculations were used to refine molecular structures of intermediates and obtain their geometries. Toxicity of PIN and its mixtures formed during photocatalytic degradation were investigated using mammalian cell lines (H-4-II-E, HT-29, and MRC-5). The H-4-II-E cell line was the most sensitive to PIN and its photodegradation mixtures. The computational results were combined with the experimental data on the amounts of degradation intermediates for determination of the intermediates that were principally responsible for the toxicity. Intermediate with two hydroxyl groups, positioned on indole ring in meta and para positions, was proposed as the one with the highest contribution to toxicity.

The impact of humic acid on toxicity of individual herbicides and their mixtures to aquatic macrophytes.

This study investigates the impact of humic acid (HA) on the toxicity of selected herbicides and their binary mixtures to aquatic plants. The focus was on two auxin simulators (2,4-D and dicamba) and two photosynthetic inhibitors (atrazine and isoproturon). The results suggested that the addition of HA to the standard synthetic medium does not affect Lemna minor growth nor the toxicity of atrazine, but increases the toxicity of 2,4-D and the binary mixture of atrazine and 2,4-D. The addition of HA to the standard synthetic medium reversibly decreased the growth (biomass) of Myriophyllum aquaticum and enhanced the toxicity of individually tested herbicides (isoproturon and dicamba) as well as their binary mixture. The results showed delayed toxic effects of auxin simulators, especially 2,4-D in the Lemna test. The recovery after the exposure to individual photosystem II inhibitors (atrazine and isoproturon) is fast in both plant species, regardless of the presence of HA. In the case of selected mixtures (atrazine + 2,4-D and isoproturon + dicamba), recovery of both plant species was noted, while the efficiency depended on the herbicide concentration in the mixture rather than the presence or absence of HA.

Arsenic adsorption on Fe-Mn modified granular activated carbon (GAC-FeMn): batch and fixed-bed column studies.

Granular activated carbon (GAC) was modified with Fe-Mn binary oxide to produce a novel effective hybrid adsorbent (GAC-FeMn) for simultaneous removal of As(III) and As(V) from water. After characterization (including BET, SEM/EDS and XRD analyses) of the raw and modified GAC, FTIR analysis before and after As removal showed that ligand exchange was the major mechanism for As removal on GAC-FeMn. Sorption kinetics followed pseudo-second order kinetics for both As(III) and As(V) and were not controlled by intraparticle diffusion. Batch equilibrium experiments yielded adsorption capacities for As(III) and As(V) of 2.87 and 2.30 mg/g, and demonstrated that better sorption was achieved at low pH. Of the competitive anions investigated (PO43-, SiO32-, CO32-, SO42-, NO3-, Cl-), phosphate had the greatest negative effect on As(III) and As(V) adsorption. Three sorption/desorption cycles were conducted in continuous column tests with a real arsenic contaminated groundwater, with subsequent TCLP leaching tests confirming the stability of the spent sorbent. In the column tests, breakthrough curves were also obtained for phosphates, which were present at a relatively high concentration (1.33 mg/L) in the investigated groundwater. The phosphates limited the effective operational bed life of GAC-FeMn for arsenic removal. Nonetheless, the maximum arsenic adsorption capacities for GAC-FeMn obtained by the Thomas model during the three sorption cycles were high, ranging from 18.8 to 29.8 mg/g, demonstrating that even under high phosphate loads, with further process improvements, GAC-FeMn may provide an excellent solution for the economic removal of arsenic from real groundwaters.

Lindane and hexachlorobenzene sequestration and detoxification in contaminated sediment amended with carbon-rich sorbents.

Sediment represents a sink for toxic and persistent chemicals such as hexachlorobenzene (HCB) and lindane (γ-HCH). This paper investigates the possibility of reducing the risks associated with the presence of these pollutants in sediments by amending the sediment with carbon-rich materials (activated carbon (AC) and humus (HC)) to sequester the contaminants and render them biologically unavailable. The effects of the dose and contact time between the sediment and the carbon-rich amendments on the effectiveness of the detoxification are estimated. Four doses of carbon-rich amendments (0.5-10%) and four equilibration contact times (14-180 days) were investigated. Results have shown that the bioavailable fraction of γ-HCH and HCB decreased significantly in comparison to the unamended sediment. Regarding the AC amendments, almost 100% for both compounds; and for HC amendments around 95% for γ-HCH, and 75% for HCB. Aging caused further reductions in the bioavailable fraction, compared to the untreated sediment. Phytotoxicity tests showed that Zea mays accumulated significantly higher amount of γ-HCH and HCB from unamended sediment, comparing to Cucurbita pepo and Lactuca sativa. Toxicity of HC and AC amended sediment assessed by Vibrio fischeri luminescence inhibition test and by measuring Zea mays germination and biomass yield was significantly reduced in the amended sediment samples. γ-HCH and HCB accumulation in the Zea mays biomass in the unamended sediment were a significantly higher than in the all HC and AC amended sediment. Both sorbents show potential to be used as remediation agents for organically contaminated sediment, but AC exhibited the better performance.

Environmental mixture with estrogenic activity increases Hsd3b1 expression through estrogen receptors in immature rat granulosa cells.

Humans are exposed not only to single endocrine disruptors, but also to chemical mixtures that can adversely affect their reproductive health. Steroidogenesis in reproductive tissues is emerging as the key target of endocrine disruptor action. Here, we analyzed the effect of environmental chemical mixtures with estrogenic activity on steroidogenic processes in immature rat granulosa cells and whether the observed steroidogenic effects were mediated through estrogen receptors. Extracts from untreated wastewater were prepared by solid-phase extraction and silica gel fractionation. ER-CALUX assay showed that the polar fractions of wastewater exerted different levels of estrogenic activity. Exposure of immature granulosa cells to the polar fraction exerting 9 ng of 17ß-estradiol equivalents per liter of water of estrogenic activity increased mRNA expression of the key enzymes of progesterone biosynthetic pathway Star and Hsd3b1, but did not alter the level of Cyp19a1 and Lhr. Addition of estrogen receptor inhibitor ICI 182 780 prevented the estrogenic mixture-induced increase in Hsd3b1, but not Star mRNA level in immature granulosa cells. These results indicate that the environmental chemical mixtures with estrogenic activity exert endocrine disrupting effects by augmenting the progesterone biosynthetic pathway in immature rat granulosa cells, which is an effect achieved in part through activation of the estrogen receptors.

Removal of diclofenac from water by in/out PAC/UF hybrid process.

Results from a lab-scale investigation of a hybrid in/out ultrafiltration and powdered activated carbon adsorption PAC/UF for removal of diclofenac (c0 = 5 mg/L) are presented. The efficiency of the process was compared for single pulse and continuous carbon dosing (PAC dose 5 mg/L) in dechlorinated tap water under fluxes of 87 and 135 L/(m2 h). For higher flux conditions, it was observed that single pulse dosing has an advantage over continuous dosing procedure when comparing cycle average removal efficiency. Increase of carbon dose under these conditions increased cycle average removal only to a limited extent. PAC dose above 15 mg/L did not give improvements of the removal. Hypothesis was made that non-effective carbon distribution might be the possible reason.

Downregulation of autophagy gene expression in endometria from women with polycystic ovary syndrome.

Autophagy, a process of controlled cellular self-digestion, could be involved in cyclic remodeling of the human endometrium. We investigated endometrial mRNA expression of 23 autophagy-related (ATG) genes and transcription factors in healthy controls (n = 12) and anovulatory polycystic ovary syndrome (PCOS) patients (n = 24), as well as in their subgroup (n = 12) before and after metformin treatment. The mRNA levels of transcription factor forkhead box protein O1 (FOXO1) and several molecules involved in autophagosome formation (ATG13, RB1-inducible coiled-coil 1), autophagosome nucleation (ATG14, beclin 1, SH3-domain GRB2-like endophilin B1), autophagosome elongation (ATG3, ATG5, γ-aminobutyric acid receptor-associated protein - GABARAP), and delivery of ubiquitinated proteins to autophagosomes (sequestosome 1), were significantly reduced in anovulatory PCOS compared to healthy endometrium. Free androgen index, but not free estrogen index, insulin levels, or body mass index, negatively correlated with the endometrial expression of ATG3, ATG14, and GABARAP in PCOS patients. Treatment of PCOS patients with metformin (2 g/day for 3 months) significantly increased the endometrial mRNA levels of FOXO1, ATG3, and UV radiation resistance-associated gene. These data suggest that increased androgen availability in PCOS is associated with metformin-sensitive transcriptional downregulation of endometrial autophagy.

Response surface methodology investigation into the interactions between arsenic and humic acid in water during the coagulation process.

Interactions between arsenic and natural organic matter (NOM) are key limiting factors during the optimisation of drinking water treatment when significant amounts of both must be removed. This work uses Response Surface Methodology (RSM) to investigate how they interact during their simultaneous removal by iron chloride coagulation, using humic acid (HA) as a model NOM substance. Using a three factor Box-Behnken experimental design, As and HA removals were modelled, as well as a combined removal response. ANOVA results showed the significance of the coagulant dose for all three responses. At high initial arsenic concentrations (200µg/l), As removal was significantly hindered by the presence of HA. In contrast, the HA removal response was found to be largely independent of the initial As concentration, with the optimum coagulant dose increasing at increasing HA concentrations. The combined response was similar to the HA removal response, and the interactions evident are most interesting in terms of optimising treatment processes during the preparation of drinking water, highlighting the importance of utilizing RSM for such investigations. The combined response model was successfully validated with two different groundwaters used for drinking water supply in the Republic of Serbia, showing excellent agreement under similar experimental conditions.