Spectral characterization, degradation behavior, quenching, and semi-quantification of fluoroquinolone antibiotics in the antibiotic-humic mixture using fluorescence spectroscopy.

Antibiotics, one of the significant emerging contaminants, are intensifying their continual spread out into the environment and affecting human health and the ecosystem in the developing country Bangladesh. This study characterizes widely used fluoroquinolone (FQ) antibiotics, formulates the method to spectrally distinguish them from ubiquitous, and important reactive, adsorbent, and altering catalytic macromolecule humic substances (HS), and further quantifies them using fluorescence spectroscopy. The presence of identical fluorophore at Excitation/Emission = 225-230/285-295 nm wavelength, possession of fluorescence spectra at short emission wavelength (<350 nm) during 275 nm excitation, different emission maxima, and various fluorescing components in antibiotics identified through three-dimensional excitation-emission matrix (EEM) and parallel factor analysis (PARAFAC) models distinguished them from the humic substance as well as from each other. Stern-Volmer equation and its modified version were applied to identify quenching and binding capability, and fluorescence intensity quenching rate of antibiotics and humic in their mixture. Unlike poor and inconsistent quenching mechanisms of humic, FQ antibiotics reduced HS intensity throughout the entire photo-irradiation experiment affirming the functioning of the stable quenching methods. Static quenching of fluorophores was identified from the redshift of excited wavelength on the electronic ground state. Temperature differences during daylight and dark conditions played contrasting roles during the fluorescence quenching of FQ. Unique spectral response at emission wavelength < 350 nm during 275 nm excitation in FQ was considered as its least intensity in the antibiotic-humic mixture and was also used to formulate distinct spectral pattern of each FQ antibiotic. The study also identified the traces of FQ antibiotics with various intensities at different lakes in Bangladesh.

Distribution, characteristics and fate of fluorescent dissolved organic matter (FDOM) in the Bay of Bengal.

The Bay of Bengal (BoB) is the largest sink to retain discharges from major rivers and the Sundarbans Mangrove Forest in Bangladesh and upholds significant ecological and resource diversity. This study aims to characterize, and identify sources, spatial dynamics, and the fate of the principal ecological web driver that is fluorescent dissolved organic matter (FDOM) in the BoB using advanced techniques of excitation-emission matrix (EEM) fluorescence spectroscopy and multivariate parallel factor (PARAFAC) analyses. The identified four protein-, two humic- and one detergent-like FDOM components mostly showed higher abundance in the shallow water than deep unlike a protein-like component. Such exceptional protein-like component was identified to form colloidal structure under elevated salinity in deep water. Autochthonous humic-like FDOM originated from primary production and water temperature counteracted microbial polymerization in shallow and deep water, respectively. The annual mass deposition indicated the influx of anthropogenic pollutants from both terrestrial and internal marine systems.

Diurnal and seasonal variations of pCO2 and fluorescent dissolved organic matter (FDOM) in different polluted lakes.

This study aimed to assess pollution and daily-to-seasonal dynamics of the partial pressure of CO2 (pCO2) and CO2 degassing flux concerning the fluorescent dissolved organic matter (FDOM) from tropical lakes. A membrane-enclosed pCO2 sensor and water quality multimeter analyzer was deployed to continuously record daily and seasonal variations in pCO2 and CO2 degassing flux in three lakes in Savar, Dhaka. During both wet and dry seasons, all lake water was supersaturated with CO2 in contrast to the atmospheric equilibrium (~400 µatm). The pCO2 values in the lake water during the dry season were relatively low in comparison, and the pCO2 levels in the wet season were much higher due to external inputs of organic matter from watersheds and direct inputs of CO2 from soils or wetlands. The estimated water-to-air CO2 degassing flux in the different levels of polluted lakes varies with the pollution context. Study areas calculated the carbon flux and three lakes released respectively 86.75×107g CO2 year-1, 13.8×107g CO2 year-1, and 9.17×107g CO2 year-1. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy combined with parallel factor (PARAFAC) analysis was used to investigate the distributions of fluorescent components in DOM. EEM-PARAFAC analysis identified humic-like, fulvic-like, protein-like, and more tyrosine-like FDOM components and their environmental dynamics. Terrestrial DOM may provide inputs to the terrestrial humic-like component in the lake water. In contrast, the biological activity of plankton-derived FDOM is the most likely source for the autochthonous humic-like component. FDOM and DO concentrations have negative correlations with pCO2, indicating that when the FDOM and DO level is decreased, the amount of pCO2 values increases.

Biogeochemistry of the dissolved organic matter (DOM) in the estuarine rivers of Bangladesh-Sundarbans under different anthropogenic influences.

The Bangladesh-Sundarbans is the Outstanding Universal Value (OUV) articulated by UNESCO, is under different anthropogenic stress. The present study focused on the status of estuarine biogeochemistry of the dissolved organic matter (DOM) of the Bangladesh-Sundarbans using different optical methods. Four fluorophores: Peak A (230-265/408-488 nm), Peak M (290/414 nm), Peak C (365/488 nm), and Peak W (320/410 nm), and three fluorescent dissolved organic matter (fDOM) components (two humic-like, one detergent-like) were identified in the Sundarban mangrove Rivers by Excitation-Emission Matrix (EEM) and Parallel Factor (PARAFAC) analyses. Among the three components, the terrestrial-derived humic-like Component had a high intensity in five samples among six in the Bangladesh-Sundarbans. The total fluorescent intensity and calculated dissolved organic carbon (DOC) concentration were maximum in Harbaria and minimum in Kotka and Dublar char, respectively. Synchronous fluorescence spectroscopy (SFS) identified protein-like component besides humic-like DOM. The optical indices described that natural fDOM components were from terrestrial sources, were matured, and autochthonous fDOM production was low. The DOM components were relatively lower in molecular size and aromaticity in Harbaria. However, water samples in Harbaria contained organometallic compounds that had much absorbance at 254 nm wavelength. DOM components had low energy and more π-conjugated molecules in structure in the Dublar char and Kotka. Components in Dublar char had comparatively higher molecular size and weight than other sampling stations. The Harbaria and Mongla port contained more hydrophobic and less polar substances than other stations. This study will firmly add diversified notions to future research regarding mangrove forest.

Temporal changes in hydrochemistry and DOM characteristics of the Brahmaputra River: implication to the seasonality of water quality.

Fluorescent dissolved organic matter (fDOM) in the Brahmaputra River water was characterized using excitation-emission matrix fluorescence spectroscopy (EEM) and parallel factor analysis (PARAFAC) model. EEM and PARAFAC model identified five fluorophores (Peak A, C, M, T, Tuv) and four fDOM components (two humic-, tryptophan-, and tyrosine-like) in the Brahmaputra River water. DOC varied between 0.8 and 3.9 mg/L and along with the intensities of the fDOM components showed higher concentration in the pre-monsoon and monsoon than post-monsoon. Higher biological oxygen demand (BOD) and chemical oxygen demand (COD) confirmed the presence of a high amount of organic pollutants in the Brahmaputra River of Bangladesh. Cations and anions concentrations were comparatively lower in the monsoon and pre-monsoon compared to post-monsoon. Mg2+, Na+, and HCO3- ions were predominant; catchments were carbonate mineral-dominated; and the abundance of Na+ and SO42- ions described the presence of uncommon dissolution in the Brahmaputra River. Optical indices described that fDOM components were less aromatic, had low molecular size and weight, terrestrial and biological derived, and were largely affected by microbial decomposition. The Brahmaputra River water was in the higher microbial risk at the pre-monsoon and monsoon than the post-monsoon of the year. Entropy and Technique for Order of Preference by Similarity to Ideal Solution (TOPSIS) methods based water quality index (WQI) was developed using PARAFAC components matrix of DOM. Newly derived WQI showed high seasonal variability of water quality in the Brahmaputra River due to the changes in local hydro-climate.

Source apportionment, ecological, and human health risks of toxic metals in road dust of densely populated capital and connected major highway of Bangladesh.

This study investigates pollution levels, source apportionment, ecological, and human health risks associated with toxic metals (Pb, As, Hg, Cr, and Cd) in road dust from the most populated Dhaka city and a connected major highway in Bangladesh. The mean concentration of Pb, Hg, and Cd were 1.3, 29.3, and 13.2 times higher than their corresponding background values with spatially uneven distribution all over the study area. Metal pollution indices, the geo-accumulation index (Igeo), NIPI, and PI, indicated extreme contamination at many sites depending on local environmental factors. The potential ecological risk ([Formula: see text] revealed that 84% and 54% of samples showed the extreme ecological risk for Hg and Cd pollution, respectively. On the other hand, the potential ecological risk index (PERI) and Nemerow integrated risk index (NIRI) showed that most sampling sites suffered high to extreme ecological risk. Source apportionment using positive matrix factorization (PMF) identified coal combustion, and gasoline (50.14%), traffic exhaust (35.26%), and industrial and agriculture activity (14.60%) were the main source of toxic metals of the study area. Non-carcinogenic health risk indicated that adults are more vulnerable than children, and hazard index (HI) of Hg for both age groups and Cd for adults were significantly higher than the safe level. The carcinogenic risk (CR) levels of toxic metals were acceptable (10-6 to 10-4), although the maximum limit of Cr for children and As for adults was close to the unacceptable limit (10-4). Continual exposure to toxic metals through road dust might develop lifetime cancer risk in local inhabitants.

Salinity-induced fluorescent dissolved organic matter influence co-contamination, quality and risk to human health of tube well water, southeast coastal Bangladesh.

Salinity in the drinking water of coastal Bangladesh results from a severe socio-economic, environmental and human health safety crisis. In this paper, we analyzed 120 tube well water samples from southeast coastal Bangladesh for eight trace metals (TMs). Contamination, quality and risk of TMs to human health of tube well water influenced by salinity-induced fluorescent dissolved organic matter (FDOM) were assessed using multiple pollution indices, GW quality index (GWQI), traditional health risk, and PARAFAC models. The mean values of EC, Fe, Cd, Cr, and As surpassed the limit set by local and international standards with significant spatial variations. The results of the GWQI showed that 52.5% of the samples were within the moderate-poor quality range in the study region. PARAFAC modeling identified three groundwater FDOM constituents with a coupling of humic acid (HA), fulvic acid (FA), and degraded fulvic acid (DFA)-like substances. Moreover, the positive correlations among EC, TMs, HA, FA, and DFA proved that salinity-induced FDOM had significant contributions to the dissolution potential of contaminants in the aquifer, hence increased the mobilization of TMs. Health risk models suggested that children are more susceptible to the non-carcinogenic and carcinogenic risks than adults at the community level. The carcinogenic risks of Cd, As, Pb, and Cr via oral exposure pathway indicated the highest carcinogenic risks for both adults and children. The findings also indicated that the salinity-derived FDOM-TMs complex is the key driver to groundwater co-contaminations and elevated health impacts. Besides, high concentrations of Fe and As are the key causal issues for sustainable water safety. Thus, strict water management and monitoring plans require preventing these contaminants for sustainable community well-being in the coastal region.

Appraisal of probabilistic human health risks of heavy metals in vegetables from industrial, non-industrial and arsenic contaminated areas of Bangladesh.

Monitoring of heavy metal content in commonly consumed vegetables is of high priority for food safety, and public health risk assessment. Vegetables were collected from industrial, non-industrial, arsenic contaminated region and one of popular vegetable markets of Bangladesh for analyzing heavy metals (As, Cd, Pb, Cu and Zn) using Atomic Absorption Spectroscopy (AAS) with standard digestion procedure. Results showed significant variations of heavy metal content among vegetables and most of cases the metals (except Cu and some of Zn) revealed several times higher concentrations than that of maximum permissible level (MPL) values, which indicated the vegetables were contaminated through either natural or anthropogenic activities. The dietary intake of metals are responsible for association of health risk that evaluated by target hazard quotient (THQ), hazard index (HI), and target carcinogenic risk (TR) calculations. Estimated daily intake (EDI) for all metals were below the maximum tolerable daily intake (MTDI) values of all vegetables. The THQs for single metals were less than 1 (except As and Pb for few vegetables), indicating the inhabitant would not possess health hazard for single metal through vegetables consumption. However, the total target hazard quotient (TTHQ) of all metals were >1 (except Cu and Zn for industrial and non-industrial sites), suggesting potential health risk. HI values were found more than 1 (36.24 for industrial site, 16.74 for non-industrial site, and 15.03 for local market) representing the selected vegetables intake might be affected quality of food safety of densely populated Bangladesh. The probabilistic risk, individual, and total cancer risk (TR) for As and Pb were exceeded the threshold level (10-4) and safe limit (10-6), respectively, indicating peoples who have been consuming these vegetables long time, they might be exposed by lifetime cancer risk. Sensitivity analysis revealed that the metal concentration has high influence on carcinogenic risks.

Variability of water quality and metal pollution index in the Ganges River, Bangladesh.

The Ganges River is one of the biggest transboundary streams in the Indian sub-continent. The significant part of this waterway channel drains one of the most densely populated areas on the planet so it is unequivocally influenced by human activities. Unprecedented high-temporal-resolution samples were collected for investigating the seasonal variability of water quality. Water quality index (WQI) reveals large seasonal variation among three major seasons and also indicates that the river water is not suitable for drinking and other household uses. The dominant water facies is bicarbonate (HCO3-). The water quality indices, %Na, Kelley's ratio (KR), sodium adsorption ratio (SAR), and magnesium adsorption ratio (MAR), reveal that the water is appropriate for irrigation. The permeability index (PI) indicated that the water is moderate to poorly useable for agricultural purposes. Heavy metals concentrations demonstrated significant seasonal variations with high concentrations during the monsoon due to flushing of pollutants from catchment areas by intense monsoonal precipitations. In addition, local activities such as oil spills from the boat, vehicle washing water, and agricultural runoff may also added pollutants. The single-factor pollution index (Ii) and Nemerow pollution index (Ni) exhibits minor pollution. The values of heavy metal pollution index (HPI) are far below than the critical limit (100) for the studied month, although relatively higher HPI values found for April, August, and November than other months might come from domestic wastes and agricultural activities. The heavy metal evaluation index (HEI) values of all the months indicated a low degree of pollution. Even though the river water pollution level is low, the authority should take proper management and monitoring strategy for sustainable use.