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 Banana Peel Activated Carbon for Removing Pharmaceutical Pollutants from Different Waters: Production, Characterization, and Application.

Due to the growing concerns about pharmaceutical contamination and its devastating impact on the economy and the health of humans and the environment, developing efficient approaches for removing such contaminants has become essential. Adsorption is a cost-effective technique for removing pollutants. Thus, in this work, banana peels as agro-industrial waste were utilized for synthesizing activated carbon for removing pharmaceuticals, namely amoxicillin and carbamazepine from different water matrices. The chemically activated carbon by phosphoric acid (H3PO4) was carbonized at temperatures 350 °C, 450 °C and 550 °C. The material was characterized by several techniques such as scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), Boehm titration, point of zero charge (pHPZC), BET surface area (SBET), the proximate and ultimate analyses, X-ray powder diffraction (XRD), and thermos-gravimetric analysis (TGA). The SEM of banana peel activated carbon (BPAC) depicted a semi-regular and heterogeneous morphology, characterized by an abundance of pores with diverse forms and sizes. Boehm titration revealed an increase in the amounts of acidic groups by 0.711 mmol/g due to activation by H3PO4. FTIR recorded different peaks suggesting significant modifications in the spectroscopic characteristics of the BPAC surface due to the successful activation and adsorption of the pollutant molecules. The pHpzc of BPAC was calculated to be 5.005. The SBET surface area dramatically increased to 911.59 m2/g after the activation. The optimum conditions were 25 °C, a materials dosage of 1.2 g/L, a saturation time of 120 min, a pollutants mixture of 25 mg/L, and a pH of 5. Langmuir exhibits a slightly better fit than Freundlich with a low value of the residual sum of squares (SSE) and the data were better fitted to the pseudo-second-order kinetic. Furthermore, the efficacy of BPAC in eliminating pharmaceuticals from Milli Q water, lake water, and wastewater was successfully investigated over the seven cycles. The results of the present work highlighted a potential usage of agro-industrial waste in eliminating organic micropollutants while exhibiting sustainable management of this waste.

A novel and sustainable composite of L@PSAC for superior removal of pharmaceuticals from different water matrices: Production, characterization, and application.

This study endeavors to develop cost-effective environmentally friendly technology for removing harmful residual pharmaceuticals from water and wastewater by utilizing the effective adsorption of pistachio shell (PS) biochar and the degradation potency of laccase immobilized on the biochar (L@PSAC). The carbonatization and activation of the shells were optimized regarding temperature, time, and NH4NO3/PS ratio. This step yielded an optimum PS biochar (PSAC) with the highest porosity and surface area treated at 700 °C for 3 h using an NH4NO3/PS ratio of 3% wt. The immobilization of laccase onto PSAC (L@PSAC) was at its best level at pH 5, 60 U/g, and 30 °C. The optimum L@PSAC maintained a high level of enzyme activity over two months. Almost a complete removal (>99%) of diclofenac, carbamazepine, and ciprofloxacin in Milli-Q (MQ) water and wastewater was achieved. Adsorption was responsible for >80% of the removal and the rest was facilitated by laccase degradation. L@PSAC maintained effective removal of pharmaceuticals of ≥60% for up to six treatment cycles underscoring the promising application of this material for wastewater treatment. These results indicate that activated carbon derived from the pistachio shell could potentially be utilized as a carrier and adsorbent to efficiently remove pharmaceutical compounds. This enzymatic physical elimination approach has the potential to be used on a large-scale.

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.

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.

Ketoprofen and aspirin removal by laccase immobilized on date stones.

In recent years, enzymatic remediation/biocatalysis has gained prominence for the bioremediation of recalcitrant chemicals. Laccase is one of the commonly investigated enzymes for bioremediation applications. There is a growing interest in immobilizing this enzyme onto adsorbents for achieving high pollutant removal through simultaneous adsorption and biodegradation. Due to the influence of the biomolecule-support interface on laccase activity and stability, it is crucial to functionalize the solid carrier prior to immobilization. Date stone (PDS), as an eco-friendly, low-cost, and effective natural adsorbent, was utilized as a carrier for laccase (fungus Trametes versicolor). After activating PDS through chemical treatments, the surface area increased by thirty-six-fold, and carbonyl groups became more prominent. Batch experiments were carried out for ketoprofen and aspirin biodegradation in aqueous solutions. After six cycles, the laccase maintained 54% of its original activity confirmed by oxidation tests of 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) (ABTS). In addition, the storage, pH, and thermal stability of immobilized laccase on functionalized date stone (LFPDS) were found to be superior to that of free laccase, demonstrating its potential for ongoing applications. In the aqueous batch mode, this immobilized laccase system was used to degrade 25 mg L-1 of ketoprofen and aspirin, resulting in almost complete removal within 4 h of treatment. This study reveals that agricultural wastes such as date stone can successfully be valorized through simple activation techniques, and the final product can be used as an adsorbent and substrate for immobilization enzyme. The high efficiency of the LFPDS in removing ketoprofen and aspirin highlights the potential of this technology for removing pharmaceuticals and merits its continued development.