Seasonal variation and concentration of PAHs in Lake Balaton sediment: A study on molecular weight distribution and sources of pollution.

The temporal and spatial variations of 16 Polycyclic Aromatic Hydrocarbons (PAHs) were examined at multiple sites around Lake Balaton from February 2023 to January 2024. The results indicated that the concentrations of PAHs in sediment were high during the winter months, 448.35 to 619.77 ng/g dry weight, and low during the summer months, 257.21 to 465.49 ng/g dry weight. The concentration of high molecular weight PAHs (HMWPAHs), consisting of 5-6 rings, was greater than that of low molecular weight PAHs (LMWPAHs), which had 2-3 rings. The total incremental lifetime cancer risk (ILCR) for both dermal and ingestion pathways was high for both adults and children during the four seasons, with the highest records as the following: winter > spring > summer > autumn. The ecological effects of the 16 PAHs were negligible except for acenaphthylene (Acy) and fluorene (Fl), which displayed slightly higher concentrations during the autumn and spring, respectively.

Temporal and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in the Danube River in Hungary.

The Danube is a significant transboundary river on a global scale, with several tributaries. The effluents from industrial operations and wastewater treatment plants have an impact on the river's aquatic ecosystem. These discharges provide a significant threat to aquatic life by deteriorating the quality of water and sediment. Hence, a total of 16 Polycyclic Aromatic Hydrocarbons (PAHs) compounds were analyzed at six locations along the river, covering a period of 12 months. The objective was to explore the temporal and spatial fluctuations of these chemicals in both water and sediment. The study revealed a significant fluctuation in the concentration of PAHs in water throughout the year, with levels ranging from 224.8 ng/L during the summer to 365.8 ng/L during the winter. Similarly, the concentration of PAHs in sediment samples varied from 316.7 ng/g in dry weight during the summer to 422.9 ng/g in dry weight during the winter. According to the Europe Drinking Water Directive, the levels of PAHs exceeded the permitted limit of 100 ng/L, resulting in a 124.8% rise in summer and a 265.8% increase in winter. The results suggest that the potential human-caused sources of PAHs were mostly derived from pyrolytic and pyrogenic processes, with pyrogenic sources being more dominant. Assessment of sediment quality standards (SQGs) showed that the levels of PAHs in sediments were below the Effect Range Low (ERL), except for acenaphthylene (Acy) and fluorene (Fl) concentrations. This suggests that there could be occasional biological consequences. The cumulative Individual Lifetime Cancer Risk (ILCR) exceeds 1/104 for both adults and children in all sites.

A sustainable nano-hybrid system of laccase@M-MWCNTs for multifunctional PAHs and PhACs removal from water, wastewater, and lake water.

This study examined the use of modified multiwall carbon nanotubes (M-MWCNTs) with immobilized laccase (L@M-MWCNTs) for removing ciprofloxacin (Cip), carbamazepine (Cbz), diclofenac (Dcf), benzo[a]pyrene (Bap), and anthracene (Ant) from different water samples. The synthesized materials were characterized using an array of advanced analytical techniques. The physical immobilization of laccase onto M-MWCNTs was confirmed through Scanning electron microscope (SEM)-dispersive X-ray spectroscopy (EDS) analysis and Brunner-Emmet-Teller (BET) surface area measurements. The specific surface area of M-MWCNTs decreased by 65% upon laccase immobilization. There was also an increase in nitrogen content seen by EDS analysis asserting successful immobilization. The results of Boehm titration and Fourier transform infrared (FTIR) exhibited an increase in acidic functional groups after laccase immobilization. L@M-MWCNTs storage for two months maintained 77.8%, 61.6%, and 57.6% of its initial activity for 4 °C, 25 °C, and 35 °C, respectively. In contrast, the free laccase exhibited 55.3%, 37.5%, and 23.5% of its initial activity at 4 °C, 25 °C, and 35 °C, respectively. MWCNTs improved storability and widened the working temperature range of laccase. The optimum removal conditions of studied pollutants were pH 5, 25 °C, and 1.6 g/L of M-MWCNTs. These parameters led to >90% removal of the targeted pollutants for four treatment cycles of both synthetic water and spiked lake water. L@M-MWCNTs demonstrated consistent removal of >90% for up to five cycles even with spiked wastewater. The adsorption was endothermic and followed Langmuir isotherm. Oxidation, dehydrogenation, hydroxylation, and ring cleavage seem to be the dominant degradation mechanisms.

A sustainable and highly efficient fossil-free carbon from olive stones for emerging contaminants removal from different water matrices.

The olive stone is a large waste product of the olive oil extraction industry. The present study investigates developing activated carbon from olive stone waste (OSAC) to remove pharmaceuticals from water. Different temperatures and olive stone: KOH ratios were studied. The OSAC produced at 750 °C and 1:3 ratio was found to have the highest porosity and surface area and was tested in the adsorption process. Diclofenac and ciprofloxacin were selected as model contaminants. The adsorption process was optimized with regards to OSAC dosage, pH, temperature, and initial concentration of adsorbate. The OSAC was found to be effective for a wide pH range (2-11) with an optimum dosage of 1 g/L at 25 °C. The pharmaceuticals were almost completely removed in 75 min. The adsorption was endothermic and followed first-order kinetics with physical mechanisms such as electrostatic possibly being the main driver. The optimum conditions were applied to test the removal of diclofenac and ciprofloxacin in synthetic water, lake water (Lake Balaton, Hungary) and secondary wastewater for seven cycles. There was little difference between the removal of the tested water matrices highlighting the potency of OSAC as an adsorbent for pharmaceutical removal in industrial applications. The removal dropped from >99% for the first cycle to 20-30% for the seventh cycle.

Anticipated impacts of climate change on the structure and function of phytobenthos in freshwater lakes.

Climate change threatens surface waters worldwide, especially shallow lakes where one of the expected consequences is a sharp increase in their water temperatures. Phytobenthos is an essential, but still less studied component of aquatic ecosystems, and it would be important to learn more about how global warming will affect this community in shallow lakes. In this research, the effects of different climate change scenarios (SSP2-4.5 and SSP5-8.5, as intermediate and high emission scenarios) on the structure and function of the entire phytobenthos community using species- and trait-based approaches were experimentally investigated in an outdoor mesocosm system. Our results show that the forecasted 3 °C increase in temperature will already exert significant impacts on the benthic algal community by (1) altering its species and (2) trait composition (smaller cell size, lower abundance of colonial and higher of filamentous forms); (3) decreasing Shannon diversity; and (4) enhancing the variability of the community. Higher increase in the temperature (+5 °C) will imply more drastic alterations in freshwater phytobenthos by (1) inducing very high variability in species composition and compositional changes even in phylum level (towards higher abundance of Cyanobacteria and Chlorophyta at the expense of Bacillariophyta); (2) continuing shift in trait composition (benefits for smaller cell volume, filamentous life-forms, non-motile and weakly attached taxa); (3) further reducing the functional diversity; (4) increasing biofilm thickness (1.4 µm/°C) and (5) decreasing maximum quantum yield of photosystem II. In conclusion, already the intermediate emission scenario will predictably induce high risk in biodiversity issues, the high emission scenario will imply drastic impacts on the benthic algae endangering even the function of the ecosystem.

Efficient removal of pharmaceutical contaminants from water and wastewater using immobilized laccase on activated carbon derived from pomegranate peels.

In this study, pomegranate peels (PPs) as an abundant fruit processing waste was used to produce cost-effective, eco-friendly, and high-quality activated carbon. The produced carbon (fossil free activated carbon) was used for immobilizing laccase to remove a range of emerging pollutants namely diclofenac, amoxicillin, carbamazepine, and ciprofloxacin from water and wastewater. The loaded activated carbon by laccase (LMPPs) and the unloaded one (MPPs) were characterized using advanced surface chemistry analysis techniques. MPPs was found to have a porous structure with a large surface area and an abundance of acidic functional groups. Laccase immobilization reduced surface area but added active degradation sites. The optimal immobilization parameters were determined as pH 4, 35 °C, and a laccase concentration of 2.5 mg/mL resulting in a 69.8% immobilization yield. The adsorption of the emerging pollutant onto MPPs is best characterized as a spontaneous endothermic process that adheres to the Langmuir isotherm and first-order kinetics. Using synergistic adsorption and enzymatic degradation, the target pollutants (50 mg/L) were eliminated in 2 h. In both water types, LMPPs outperformed MPPs. This study shows that pomegranate peels can effectively be harnessed as an enzyme carrier and adsorbent for the removal of emerging pollutants even from a complex sample matrix. The removal of contaminants from wastewater lasted five cycles, whereas it continued up to six cycles for water.

Ecological and human health risk assessment of polycyclic aromatic hydrocarbons (PAH) in Tigris river near the oil refineries in Iraq.

Recent Iraqi battles against ISIS in 2014 and 2015 resulted in the destruction or severe damage to several refineries' infrastructure. This, along with other factors, has led to the release and accumulation of a wide range of hazardous chemicals into the environment, for instance, polycyclic aromatic hydrocarbons (PAH). Thus, for the first time, a comprehensive 16 PAHs measurements campaign over the course of six months near the oil refineries along the Tigris River and its estuaries was investigated. The 16 PAHs concentrations in surface water and the sediments for the following oil refineries: Baiji, Kirkuk, Al-Siniyah, Qayyarah, Al-Kasak, Daura, South Refineries Company, and Maysan were examined. The overall findings indicated that the 16 PAHs concentrations ranged from 567.8 to 3750.7 ng/L for water and 5619.2-12795.0 ng/g for sediment. Water samples in South Refineries Company recorded the highest PAH concentrations while Baiji oil refinery registered the highest PAH concentrations in the sediment samples. The percentages of high molecular weight PAH (5-6 rings) in water and sediment samples were the highest, ranging from 49.41% to 81.67% and from 39.06% to 89.39% of total PAH for water and sediment, respectively. The majority of 16 PAHs measured in water and sediment samples of the Tigris River were derived from pyrogenic sources. Based on sediment quality guidelines (SQGs), most sites showed a possible effect range with occasional biological effects of most of the PAH concentrations in all sediments' samples. The calculated incremental lifetime cancer risk (ILCR) value was high risk with adverse health effects, including cancer.

Polycyclic aromatic hydrocarbons in the surface water and sediment along Euphrates River system: Occurrence, sources, ecological and health risk assessment.

This study presented for the first time a comprehensive measurement campaign of 16 PAHs along the Euphrates River for five months, in both water and sediment samples. Our study revealed that the PAHs contamination increased along the flow direction due to the increasing non-point pollution and the return flows of agriculture. The 5-6 rings PAHs were dominant in water and sediment samples with an average of 42 % and 50 %, respectively. The diagnostic ratios of PAHs suggest that the pollution of these compounds originated mainly from petroleum product combustions. The carcinogenic PAHs formed 46 % and 55 % of the total measured compounds in water and sediment samples, respectively, which highlights potential ecological and human health risks. Based on sediment quality guidelines (SQGs), most sites exhibit an effect range between low and medium. The calculated incremental lifetime cancer risk (ILCR) for adult and children were in the 10-2-10-3 range, which is 3-6-fold higher than what was reported in the literature. These observations call for urgent attention from environmental authorities of countries sharing this key water source in Western Asia.

Influence of magnesium concentrations on the biomass and biochemical variations in the freshwater algae, Chlorella vulgaris.

The current study deals with the biological response variations on some biochemical properties of the freshwater green algae Chlorella vulgaris by exposure to different Mg2+ concentrations (5, 10, and 15) mg/L. Physiological and biochemical parameters, including growth curve, doubling time, photosynthesis pigments, total protein and carbohydrates were investigated. Moreover, enzymatic parameters such as catalase (CAT), superoxide dismutase (SOD), and reactive oxygen species (ROS) were also examined. The maximum growth rate was 0.482/day during the 9th day with 5 mg/L Mg2+, while the minimum was 0.019/day during the 13th and 14th days with 10 mg/L Mg2+. Furthermore, doubling time ranged between 15.501 during the 13th day with 10 mg/L Mg2+, and 0.624 during the 9th day with 5 mg/L. The maximum value of chlorophyll-a was 0.157 µg/mL during the 1st day with 10 mg/L Mg2+, while the minimum was 0.062 µg/mL during the 14th day with 15 mg/L Mg2+. The carotenoid ranged between 0.029 µg/mL during the 7th day with 15 mg/L Mg2+ and 0.002 µg/mL during the 14th day. The maximum protein value was 9.620 µg/L during the 1st day with 15 mg/L Mg2+, while the minimum was 1.772 µg/L during the 14th day with 15 mg/L Mg2+. The carbohydrate showed a maximum value of 0.824 µg/mL during the 1st day with 10 mg/L Mg2+, while the minimum was 0.293 µg/mL during the 14th day with 15 mg/L. Moreover, SOD ranged between 0.884 unit/L during the 1st day with 15 mg/L Mg2+, and 0.073 unit/L as the minimum value during the 14th day with 15 mg/L Mg2+. The maximum value of ROS was 3.627 mM/mL during the 1st day with 5 and 15 mg/L Mg2+, while the minimum was 1.674 mM/mL during the 14th day with 10 mg/L. The results show that values of CAT ranged between 0.200 unit/mL during the 7th day with 10 mg/L Mg2+, and 0.010 unit/mL during the 14th day with 15 mg/L. Overall, 5 mg/L for biomass production and 15 mg/L for protein and carbohydrate production were optimum doses.

Climate change projections for Carpathian soda pans on the basis of photosynthesis evidence from typical diatom species.

The Carpathian Basin is home to a number of astatic soda pans which are especially vulnerable to the climate change due to their high degree of hydrological sensitivity. The photosynthetic plasticity of the three most dominant benthic diatom species (Nitzschia aurariae, N. reskovii, N. supralitorea) in a number of soda pans was measured, along with sulphate and chloride ion content; conductivity and temperature gradients were also recorded. On the basis of the maximal photosynthetic activity (Ps), climate models were employed to observe and predict the effects of climate change on photosynthesis over three time-spans: past (1970-2000), recent past (2005-2015) and projected future (2041-2060). Comparing the periods, it becomes apparent that climate change has a significant effect on photosynthesis and the photosynthetically active period of the Nitzschia species, the dominant primary producers in soda pans, by enhancing their photosynthetic activity and extending their vegetation period by two months. Due to the breadth of their ecological niche, the competitive advantages of the diatom species studied in the course of this research as against others are expected to prevail under the conditions predicted by the climate scenario presented here.

Trait-based diatom functional diversity as an appropriate tool for understanding the effects of environmental changes in soda pans.

Saline lakes, among the most seriously endangered ecosystems, are threatened due to climate change and human activities. One valuable feature of these environments is that they constitute areas of high biodiversity. Ecologists are, therefore, under great pressure to improve their understanding of the effects of natural and anthropogenic disturbances on the biodiversity of saline lakes. In this study, a total of 257 samples from 32 soda pans in Central Europe between 2006 and 2015 were examined. The effects of environmental variables and of geographical and limnoecological factors on functional diversity were analyzed. Furthermore, the explanatory power of the trait-based approach was assessed, and the applicability of the indices for biomonitoring purposes was determined. It was found that low habitat heterogeneity and harsh environments lead to the selection of a small number of suitable traits, and consequently, to a naturally low level of functional diversity. Anthropogenic activities enhance diversity at functional level due to the shift toward freshwater characteristics. On the regional scale, the effects of the region and status (natural, degraded, reconstructed) on diatom functional diversity were significant and more pronounced than that of the environmental and other limnoecological factors. The degree of variance found in functional diversity ascribed to environmental variables is five times greater in the case of the application of a trait-based approach, than when a taxonomic one is employed in the literature. Each of the tested functional diversity indices was sensitive to the most important environmental variables. Furthermore, these were type-specific and proved to be more complex indicators than taxonomic metrics. It is possible to suggest four functional diversity indices (FGR, FRic, FDis, and FDiv) which emphasize their independence from substrate and seasonal variations for ecological status assessment and conservation planning.

The impact of OTU sequence similarity threshold on diatom-based bioassessment: A case study of the rivers of Mayotte (France, Indian Ocean).

Extensive studies on the taxonomic resolution required for bioassessment purposes have determined that resolution above species level (genus, family) is sufficient for their use as indicators of relevant environmental pressures. The high-throughput sequencing (HTS) and meta-barcoding methods now used for bioassessment traditionally employ an arbitrary sequence similarity threshold (SST) around 95% or 97% to cluster sequences into operational taxonomic units, which is considered descriptive of species-level resolution. In this study, we analyzed the effect of the SST on the resulting diatom-based ecological quality index, which is based on OTU abundance distribution along a defined environmental gradient, ideally avoiding taxonomic assignments that could result in high rates of unclassified OTUs and biased final values. A total of 90 biofilm samples were collected in 2014 and 2015 from 51 stream sites on Mayotte Island in parallel with measures of relevant physical and chemical parameters. HTS sequencing was performed on the biofilms using the rbcL region as the genetic marker and diatom-specific primers. Hierarchical clustering was used to group sequences into OTUs using 20 experimental SST levels (80%-99%). An OTU-based quality index (IdxOTU) was developed based on a weighted average equation using the abundance profiles of the OTUs. The developed IdxOTU revealed significant correlations between the IdxOTU values and the reference pressure gradient, which reached maximal performance using an SST of 90% (well above species level delimitation). We observed an interesting and important trade-off with the power to discriminate between sampling sites and index stability that will greatly inform future applications of the index. Taken together, the results from this study detail a thoroughly optimized and validated approach to generating robust, reproducible, and complete indexes that will greatly facilitate effective and efficient environmental monitoring.

Taxonomy- or trait-based ecological assessment for tropical rivers? Case study on benthic diatoms in Mayotte island (France, Indian Ocean).

Diatom-based ecological quality assessment methods have been implemented and used regularly in the Water Framework Directive. These indices use the species' abundance profiles along a specific environmental gradient, which they aim to assess. However, this approach has several problematic issues including the unstable and fast-changing diatom taxonomy. The use of traits can be a solution if their responses to the environmental pressure are well-defined. Here, we developed taxonomy-based and trait-based diatom assemblage indices to assess the ecological status of riverine sites on a tropical island. The two indices are based on two sub-indices that measure the diatom assemblage response to a nutrient and organic matter/turbidity gradient. Both taxonomy- and trait-based indices correlated significantly with the selected environmental gradients of the test database, which was not used during index development. We showed that traits could be used for quality assessment of the Mayotte rivers and require much less effort than taxonomy-based indices. There were differences between the two types of indices, which are discussed in this paper. As a perspective for further studies, tests of trait-based indices among different eco-regions would be challenging.