A probabilistic risk assessment of heavy metal in water and sediment: An industrially affected urban river in Bangladesh.

Human welfare and biodiversity are at risk due to the deterioration of water and sediment quality. Particularly, in last few decades, global water and sediment quality degraded due to the rapid industrialization and urbanization. This study aimed to determine the concentration of nine heavy metals and metalloid (Pb, Cr, Cd, Hg, As, Mn, Ni, Cu, and Zn) and assess the ecological risks using different pollution indices (e.g., heavy metal pollution index [HPI], Nemerow pollution index [NI], geo-accumulation index [Igeo], contamination factor [CF], degree of contamination [CD] and pollution load index [PLI], ecological risk index [ERI]) in water and sediment of the Shitalakshya River, an industrially affected urban river of Bangladesh. For the first time, 20 water and sediment samples were collected across a wider geographical area of the Shitalakshya River during both monsoon and dry seasons and analyzed using the atomic absorption spectrometer. Average concentrations of heavy metals and metalloid in water were within the Bangladesh standard except for Cr (51.69 ppb) and Mn (228.20 ppb) during monsoon season, portraying potential ecological and human health risks. Besides, average concentration of Mn (549.75 and 370.93 ppb), Ni (549.75 and 370.93 ppb), and Cu (45.34 and 36.09 ppb) in sediment during both seasons were above international standard, implying risk to aquatic sediment biota. The average HPI values indicated moderate to high contamination, whereas the NI values implied polluted water in monsoon season with severe pollution in port area of the river. Similarly, Igeo, CF, CD, and PLI elucidated different levels of contamination in the sediment, particularly during dry season. The ERI values also referred moderate ecological risk in the sediment during dry season. Overall, our findings highlight the alarming level of heavy metal pollution in the Shitalakshya River, necessitating immediate action to protect the aquatic environment, sediment biota, and human health. PRACTITIONER POINTS: This study determined the concentration of heavy metals and metalloid in water and sediment of the Shitalakshya River, Bangladesh. The study revealed that the average concentration of Cr and Mn in water exceeded national standard, whereas Mn, Ni, and Cu in sediment exceeded international limit. Potential ecological risk of heavy metals was also assessed using different pollution indices. Calculated pollution indices indicated different degree of pollution, implying critical ecological condition due to heavy metal pollution in aquatic environment and sediment biota.

Valence and Core Photoelectron Spectra of Aqueous I3- from Multi-Reference Quantum Chemistry.

The I3- molecule is known to undergo substantial structural reorganization upon solvation by a protic solvent, e.g., water. However, the details of this process are still controversially discussed in the literature. In the present study, we combined experimental and theoretical efforts to disentangle this controversy. The valence (5p), N4,5 (4d), and M4,5 (3d) edge photoelectron spectra were measured in an aqueous solution and computed using high-level multi-reference methods. Our previous publication mainly focused on obtaining reliable experimental evidence, whereas in the present article, we focused primarily on theoretical aspects. The complex electronic structure of I3- requires the inclusion of both static and dynamic correlation, e.g., via the multi-configurational perturbation theory treatment. However, the resulting photoelectron spectra appear to be very sensitive to problems with variational stability and intruder states. We attempted to obtain artifact-free spectra, allowing for a more reliable interpretation of experiments. Finally, we concluded that the 3d Photoelectron Spectrum (PES) is particularly informative, evidencing an almost linear structure with a smaller degree of bond asymmetry than previously reported.

Probing the molecular structure of aqueous triiodide via X-ray photoelectron spectroscopy and correlated electron phenomena.

Liquid-microjet-based X-ray photoelectron spectroscopy was applied to aqueous triiodide solutions, I3-(aq.), to investigate the anion's valence- and core-level electronic structure, ionization dynamics, associated electron-correlation effects, and nuclear geometric structure. The roles of multi-active-electron (shake-up) ionization processes - with noted sensitivity to the solute geometric structure - were investigated through I3-(aq.) solution valence, I 4d, and I 3d core-level measurements. The experimental spectra were interpreted with the aid of simulated photoelectron spectra, built upon multi-reference ab initio electronic structure calculations associated with different I3-(aq.) molecular geometries. A comparison of the single-to-multi-active-electron ionization signal ratios extracted from the experimental and theoretical core-level photoemission spectra suggests that the ground state of the solute adopts a near-linear average geometry in aqueous solutions. This contrasts with the interpretation of time-resolved X-ray solution scattering studies, but is found to be fully consistent with the rest of the solution-phase I3-(aq.) literature. Comparing the results of low- and high-photon-energy photoemission measurements, we further suggest that the aqueous anion adopts a more asymmetric geometry at the aqueous-solution-gas interface than in the aqueous bulk.

Monitoring bacterial contamination of piped water supply in rural coastal Bangladesh.

Safe drinking water is scarce in southwest coastal Bangladesh because of unavailability of fresh water. Given the high salinity of both groundwater and surface water in this area, harvested rainwater and rain-fed pond water became the main sources of drinking water. Both the government and non-government organizations have recently introduced pipe water supply in the rural coastal areas to ensure safe drinking water. We assessed the bacteriological quality of water at different points along the piped water distribution system (i.e., the source, treatment plant, household taps, street hydrants, and household storage containers) of Mongla municipality under Mongla Upazila in Bagerhat district. Water samples were collected at 2-month interval from May 2014 to March 2015. Median E. coli and total coliform counts at source, treatment plant, household taps, street hydrants, and household storage containers were respectively 225, 4, 7, 7, and 15 cfu/100 ml and 42,000, 545, 5000, 6150, and 18,800 cfu/100 ml. Concentrations of both of the indicator bacteria reduced after treatment, although it did not satisfy the WHO drinking water standards. However, re-contamination in distribution systems and household storage containers indicate improper maintenance of distribution system and lack of personal hygiene.

Bicircular High-Harmonic Spectroscopy Reveals Dynamical Symmetries of Atoms and Molecules.

We introduce bicircular high-harmonic spectroscopy as a new method to probe dynamical symmetries of atoms and molecules and their evolution in time. Our approach is based on combining a circularly polarized femtosecond fundamental field of frequency ω with its counterrotating second harmonic 2ω. We demonstrate the ability of bicircular high-harmonic spectroscopy to characterize the orbital angular momentum symmetry of atomic orbitals. We further show that breaking the threefold rotational symmetry of the generating medium-at the level of either the ensemble or that of a single molecule-results in the emission of the otherwise parity-forbidden frequencies 3qω (q∈N), which provide a background-free probe of dynamical molecular symmetries.