Population exposure to emerging perfluoroalkyl acids (PFAAs) via drinking water resources: Application of multivariate statistics and risk assessment models.

This study assessed the occurrence, origins, and potential risks of emerging perfluoroalkyl acids (PFAAs) for the first time in drinking water resources of Khyber Pakhtunkhwa, Pakistan. In total, 13 perfluoroalkyl carboxylic acids (PFCAs) with carbon (C) chains C4-C18 and 4 perfluoroalkyl sulfonates (PFSAs) with C chains C4-C10 were tested in both surface and ground drinking water samples using a high-performance liquid chromatography system (HPLC) equipped with an Agilent 6460 Triple Quadrupole liquid chromatography-mass spectrometry (LC-MS) system. The concentrations of ∑PFCAs, ∑PFSAs, and ∑PFAAs in drinking water ranged from 1.46 to 72.85, 0.30-8.03, and 1.76-80.88 ng/L, respectively. Perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), and perfluoropentanoic acid (PFPeA) were the dominant analytes in surface water followed by ground water, while the concentration of perfluorobutane sulfonate (PFBS), perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), and perfluorododecanoic acid (PFDoDA) were greater than long-chain PFOA and PFOS. The correlation statistics, which showed a strong correlation (p < 0.05) between the PFAA analytes, potentially indicated the fate of PFAAs in the area's drinking water sources, whereas the hierarchical cluster analysis (HCA) and principal component analysis (PCA) statistics identified industrial, domestic, agricultural, and commercial applications as potential point and non-point sources of PFAA contamination in the area. From risk perspectives, the overall PFAA toxicity in water resources was within the ecological health risk thresholds, where for the human population the hazard quotient (HQ) values of individual PFAAs were < 1, indicating no risk from the drinking water sources; however, the hazard index (HI) from the ∑PFAAs should not be underestimated, as it may significantly result in potential chronic toxicity to exposed adults, followed by children.

Nano round polycrystalline adsorbent of chicken bones origin for Congo red dye adsorption.

Nano round polycrystalline adsorbent (NRPA) of chicken bones origin was utilize as effective adsorbent in Congo red dye removal via aqueous media. The NRPA adsorbent was prepared via thermal decomposition and its structure was investigated with the aids of Transmission Electron Microscopy, Fourier Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy, Energy Dispersive X-ray Analysis (EDX), and X-ray Diffractometer (XRD). A monophasic apatite phase was confirmed from XRD investigation, while functional groups analysis showed that NRPA possessed CO32-, PO43- and OH- absorption bands. The maximum adsorption capacities derived from Langmuir isotherm is 98.216 mg g-1. From the combined values of n from Freundlich and separation factor (RL) of Langmuir models, the adsorption of CR by NRPA is favourable. Thermodynamic values of 5.280 kJ mol-1 and 16.403 kJ mol-1 K-1 were found for ΔH° and ΔS° respectively. The entire values of ΔG° which ranges from - 35.248 to - 459.68 kJ mol-1 were all negative at different temperatures. Thus, nano polycrystalline adsorbent of chicken bone origin can serve as excellent adsorbent in Congo red dye removal from waste water.

Bioactivity properties of hydroxyapatite/clay nanocomposites.

The need for bioactive and non-toxic biomaterials is on a high demand in tissue engineering applications nowadays. Hydroxyapatite (HAp) is the chief constituent of teeth and bones in mammas. One of the major challenges with the use of HAp in engineering application is its brittleness and to overcome this, it's important to react it with a material that can enhanced it's fragility. To this end, HAp and HAp/clay nanocomposites were developed via wet chemical process to mimic natural HAp and to equally confer special properties such as mechanical properties, high surface area, crystallinity, high porosity, and biocompatibility on the biomaterial. The functional groups properties of the as-prepared nanocomposites analyzed by FT-IR showed that the HAp and clay posed reactive centers such as Al-Al-OH, Si-Si-OH, Si-O, PO43-, -OH, and Si-O-Al. The XRD results confirmed the formation of HAp/clay nanocomposite, while SEM and TEM images showed the morphologies of the prepared nanocomposites to be round shape particles. Besides, EDX result revealed the Ca/P ratio of HAp and HAp-C to be lower than that of stoichiometric ratio (1.67) which implies the presence of K, Na, Ca, Mg, Si and Al in the HAp/clay nanocomposite. The mechanical properties of the apatite were greatly enhanced by the addition of clay. The physiological behaviour of the fabricated apatite composites in saline solution showed steady increase in the values of the saline pH of the various biomolecules until day 5 and became fairly constant at day 7 with pH range of 7.30-7.38. Though the saline solution was acidic at the beginning due to dissolved carbon dioxide, the pH of the saline solution containing the nanocomposites gradually became neutral and fairly alkaline over time as a result of the presence of Lewis basis structures in the composites which helps in neutralizing the acidic solution. Furthermore, proliferation of apatites particles onto the surface of the nanocomposites was observed after treatment with simulated body fluids (SBF) media for 7 days. Thus, HAp/clay nanocomposites can be useful biomaterials in bone tissue engineering.

Heavy metals in five commonly consumed fish species from River Swat, Pakistan, and their implications for human health using multiple risk assessment approaches.

This study analyzed the levels of heavy metals bioaccumulation in commonly consumed riverine fish species, including G. cavia, T. macrolepis, G. gotyla, S. plagiostomus, and M. armatus from River Swat in Pakistan, and quantify their potential risk to children and adults in general and fisherfolk communities using multiple pollution and risk assessment approaches. The highest metal detected by inductive coupled plasma mass spectrometry (ICP-MS) was Zn, which ranged from 49.61 to 116.83 mg/kg, followed by Fe (19.25-101.33 mg/kg) > Mn (5.25-40.35 mg/kg) > Cr (3.05-14.59 mg/kg) > Ni (4.26-11.80 mg/kg) > Al (1.59-12.25 mg/kg) > Cu (1.24-8.59 mg/kg) > Pb (0.29-1.95 mg/kg) > Co (0.08-0.46 mg/kg) > Cd (0.01-0.29 mg/kg), demonstrating consistent fluctuation with the safe recommendations of global regulatory bodies. The average bioaccumulation factor (BAF) values in the examined fish species were high (BAF > 5000) for Pb, Zn, Mn, Cu, Cr, Ni, and Cd, bioaccumulate (1000 > BAF < 5000) for Co, and probable accumulative (BAF <1000) for Fe, and Al, while the overall ∑heavy metals pollution index (MPI) values were greater than one (MPI > 1) indicating sever heavy metals toxicity in G. cavia, followed by S. plagiostomus, M. armatus, G. gotyla, and T. macrolepis. The multivariate Pearson's correlation analysis identified the correlation coefficients between heavy metal pairs (NiCr, CuCr, PbCr, AlCo, CuNi, and PbNi), the hierarchical cluster analysis (CA) determined the origin by categorizing heavy metal accumulation into Cluster-A, Cluster-B, and Cluster-C, and the principal component analysis (PCA) discerned nearby weathering, mining, industrial, municipal, and agricultural activities as the potential sources of heavy metals bioaccumulation in riverine fish. As per human risk perspective, S.plagiostomus contributed significantly to the estimated daily intake (EDI) of heavy metals, followed by G.cavia > M.armatus > G.gotyla > T.macrolepis in dependent children and adults of the fisherfolk followed by the general population. The non-carcinogenic target hazard quotient (THQ) and hazard index (HI) values for heavy metal intake through fish exposure were < 1, while the carcinogenic risk (CR) for individual metal intake and the total carcinogenic risk (TCR) for cumulative Cr, Cd, and Pb intake were within the risk threshold of 10-6-10-4, suggesting an acceptable to high non-carcinogenic and carcinogenic risk for both children and adults in the fisherfolk, followed by the general population.

New and legacy pesticidal persistent organic pollutants in the agricultural region of the Sultanate of Oman.

Comprehensive air and surface soil monitoring was conducted for new and legacy organochlorine pesticides (OCPs) to fill the knowledge and data gap on the sources and fate of pesticidal persistent organic pollutants (POPs) in the Sultanate of Oman. DDTs in agricultural soil samples ranged from 0.013 to 95.80 ng/g (mean: 8.4 ± 25.06 ng/g), with a median value of 0.07 ng/g. The highest concentration was observed at Shinas, where intensive agricultural practice is prevalent. The dominance of p,p'-DDT in soil and air reflected technical DDT formulation usage in Oman. Among newly enlisted POPs, pentachlorobenzene had the maximum detection frequency in air (47%) and soil (41%). Over 90% of sites reflected extensive past use of hexachlorobenzene. Major OCP isomers and metabolites showed net volatilisation from the agricultural soil, thereby indicating concurrent emission and re-emission processes from the soil of Oman. However, the cleansing effect of oceanic air mass is the possible reason for relatively lower atmospheric OCP levels from a previous study. Although DDT displayed maximum cancer risk, the level is below the permissible limit. DDT primarily stemmed from obsolete stock and inadequate management practices. Hence, we suggest there is a need for DDT regulation in Oman.

Deoxygenation turns the coastal Red Sea lagoons into sources of nitrous oxide.

Direct measurements of dissolved N2O concentrations, fluxes and saturation percentages undertaken for the first time in two coastal lagoons - Al-Shabab and Al-Arbaeen, along the east coast of the Red Sea, revealed the region as a significant source of N2O to the atmosphere. The exacerbated dissolved inorganic nitrogen (DIN) from various anthropogenic sources led to substantial oxygen depletion in both the lagoons, which turned to bottom anoxia at Al-Arbaeen lagoon during the spring season. We assume that the accumulation of N2O is caused by nitrifier-denitrification in the hypoxic/anoxic boundaries. In fact, the results indicated that oxygen-depleted bottom waters favoured denitrification when the oxygenated surface waters recorded nitrification signals. Overall, the N2O concentration ranged from 109.4 to 788.6 nM (40.6-325.6 nM) in spring and 58.7 to 209.8 nM (35.8-89.9 nM) in winter in the Al-Arbaeen (Al-Shabab) lagoon. The N2O flux ranged from 647.1 to 1763.2 µmol m-2 day-1 (85.9 to 160.2 µmol m-2 day-1) and 112.5 to 150.8 µmol m-2 day-1 (76.1 to 88.7 µmol m-2 day-1) in the spring and winter respectively, in the Al-Arbaeen (Al-Shabab) lagoons. The ongoing developmental activities may worsen the current situation of hypoxia and associated biogeochemical feedbacks; therefore, the present results underline the need for continuous monitoring of both lagoons to restrict more severe oxygen depletion in future.