Review of soil environment quality in India near coal mining regions: current and future predictions.

Production and utilization of coal are one of the primary routes of accumulation of Toxic Elements (TEs) in the soil. The exploration of trends in the accumulation of TEs is essential to establishing a soil pollution strategy, implementing cost-effective remediation, and early warnings of ecological risks. This study provides a comprehensive review of soil concentrations and future accumulation trends of various TEs (Cr, Ni, Pb, Co, Cu, Cd, Zn, Fe, Mn, and As) in Indian coal mines. The findings revealed that average concentrations of Cr, Mn, Ni, Cu, Zn, Pb, and Co surpass India's natural background soil levels by factors of 2, 4.05, 5.32, 1.77, 9.6, and 6.15, respectively. Geo-accumulation index values revealed that 27.3%, 14.3%, and 7.7% of coal mines are heavily polluted by Ni, Co, and Cu, respectively. Also, the Potential Ecological Risk Index indicates that Cd and Ni are primary contaminants in coal mines. Besides, the health risk assessment reveals oral ingestion as the main exposure route for soil TMs. Children exhibit a higher hazard index than adults, with Pb and Cr being major contributors to their non-carcinogenic risk. In addition, carcinogenic risks exist for females and children, with Cr and Cu as primary contributors. Multivariate statistical analysis revealed that TEs (except Cd) accumulated in the soil from anthropogenic sources. The assessment of future accumulation trends in soil TE concentrations reveals dynamic increases that significantly impact both the ecology and humans at elevated levels. This study signifies a substantial improvement in soil quality and risk management in mining regions.

Development of a sulfidogenic bioreactor system for removal of co-existent selenium, iron and nitrate from drinking water sources.

The present study showed for the first time that selenium, iron, and nitrate could be simultaneously removed in a sulfidogenic bioreactor to meet drinking water standards. A bioreactor inoculated with mixed bacterial consortium was operated for around 330 days in anoxic environment at 30 °C under varying combination of influent selenate (200-1000 µg/L as selenium), and iron (3-10 mg/L) in presence of 50 mg/L of nitrate. Required amount of acetic acid (as carbon source) and sulfate were supplied and the reactor was operated at different empty bed contact time (EBCT) of 45-120 min. Along with complete removal of nitrate, the reactor removed both selenium and iron to meet the drinking water standards. Field emission transmission electron microscopy (FETEM) and X-ray diffraction (XRD) analyses confirmed the formation of selenium sulfide (SeS), achavalite (FeSe) and pyrite (FeS2), which were the possible removal mechanisms of selenium and iron. Thus, this study exhibited that selenium, iron, and nitrate can be simultaneously removed to meet the drinking water standards in a sulfidogenic bioreactor.

Bacterially-assisted recovery of cadmium and nickel as their metal sulfide nanoparticles from spent Ni-Cd battery via hydrometallurgical route.

Soaring demand for technology metals (e.g., Cd, Ni) and its ever-depleting primary resources ask for alternative recovery from secondary sources. Ni-Cd battery is one such source that can abridge the gap between demand and supply of such metals. Biogenic recovery, being environmentally benign, is explored for Cd and Ni recovery to manage the menace of spent Ni-Cd battery. Studies with 20, 40 and 60 mg/L Cd2+ initial concentrations in batch mode (in triplicates) at pH 7.0 ± 0.2, 30 ± 0.5 °C and 120 rpm were conducted using sulfate-reducing bacteria for 10 days. Analysis of extracellular polymeric substance revealed that protein secretion was enhanced, thereby forming Cd-EPS binding. Biosolids were collected and freeze-dried for morphological analysis viz. FESEM/EDX, PXRD and TEM, which revealed the formation of CdS nanoparticles (JCPDS card #00-042-1411) in range of 2-6 nm. Similarly, combined effect with 5, 10 and 20 mg/L Ni2+ at 20 mg/L Cd2+ were also investigated. Furthermore, to test the efficacy for real field application, spent Ni-Cd battery was dismantled and its powder was characterized, digested with concentrated HCl at 70 °C and was fed in batch mode after cooling, wherein nanoparticles of Ni and Cd sulfides were formed that has potential as semi-conducting material.

Concurrent removal of nitrate, arsenic and iron from simulated and real-life groundwater to meet drinking water standards: Effects of operational and environmental parameters.

The aim of this work was to study concurrent removal of nitrate, arsenic and iron in an attached growth reactor (AGR) based on bio-sulphidogenesis treating simulated and real-life ground water. A lab-scale bioreactor system was monitored for a period of 511 days under conditions identical to those prevailing at full-scale to assess the relative influence of empty bed contact time (EBCT) (20-90 min), backwash strategies (water-nitrogen and water-air), temperature (20-50 °C), pH (6.6-8.4) and shut down on reactor performance and recovery. Complete removal of nitrate (50 mg/L) and over 95% removal of iron (3 mg/L) occurred. Arsenic removal efficiency was around 99% (500 µg/L) and treated water arsenic concentration was in compliance with the World Health Organization and Indian Standard of 10 µg/L. Port sampling along the depth of bioreactor shows shifting of terminal electron accepting process zones at lower EBCT of 20 min and after air assisted backwashing. The temperature range of 20-50 °C and pH range of 6.6-8.4 were applicable for arsenic removal in natural conditions. Precipitated biosolids were analysed using electron microscopy. Biogenic sulphides resulted in the precipitation of arsenosulphides and iron sulphides, which concurrently removed arsenic and iron. This study suggests that a sulphidogenic bioreactor may help to set the basis for concurrent removal of nitrate, arsenic and iron from real-life groundwater using mixed biofilm bacterial community.

Effects of phenol on sulfate reduction by mixed microbial culture: kinetics and bio-kinetics analysis.

Mixed microbial culture collected from the wastewater treatment plant of Indian Institute of Technology Guwahati (IITG) was further grown in anaerobic condition in presence of sulfate where lactate was added as a carbon source. Sulfate addition was increased stepwise up to 1,000 mg l-1 before phenol was added at increasing concentrations from 10 mg l-1 to 300 mg l-1. Kinetics of sulfate, phenol and chemical oxygen demand reduction were studied and experimental findings were analyzed using various bio-models to estimate the bio-kinetic coefficients. This is the first detailed report on kinetics and bio-kinetic studies of sulfate reduction in presence of phenol. Experimental results showed that there was no inhibition of sulfate reduction and microbial growth up to 100 mg l-1 phenol addition. However, inhibition to different degrees was observed at higher phenol addition. The experimental data of microbial growth and substrate consumption in presence of phenol fitted well to the Edward model (R2 = 0.85, root mean square error = 0.001011) with maximum specific growth rate = 0.052 h-1, substrate inhibition constant = 88.05 mg l-1 and half saturation constant = 58.22 mg l-1. The characteristics of the cultured microbes were determined through a series of analysis and microbial tests.

Biodegradation of 4-bromophenol by Arthrobacter chlorophenolicus A6 in batch shake flasks and in a continuously operated packed bed reactor.

The present study investigated growth and biodegradation of 4-bromophenol (4-BP) by Arthrobacter chlorophenolicus A6 in batch shake flasks as well as in a continuously operated packed bed reactor (PBR). Batch growth kinetics of A. chlorophenolicus A6 in presence of 4-BP followed substrate inhibition kinetics with the estimated biokinetic parameters value of µ max = 0.246 h(-1), K i = 111 mg L(-1), K s  = 30.77 mg L(-1) and K = 100 mg L(-1). In addition, variations in the observed and theoretical biomass yield coefficient and maintenance energy of the culture were investigated at different initial 4-BP concentration. Results indicates that the toxicity tolerance and the biomass yield of A. chlorophenolicus A6 towards 4-BP was found to be poor as the organism utilized the substrate mainly for its metabolic maintenance energy. Further, 4-BP biodegradation performance by the microorganism was evaluated in a continuously operated PBR by varying the influent concentration and hydraulic retention time in the ranges 400-1,200 mg L(-1) and 24-7.5 h, respectively. Complete removal of 4-BP was achieved in the PBR up to a loading rate of 2,276 mg L(-1) day(-1).

Evaluation of 4-bromophenol biodegradation in mixed pollutants system by Arthrobacter chlorophenolicus A6 in an upflow packed bed reactor.

Bromophenol is listed as priority pollutant by U.S. EPA, however, there is no report so far on its removal in mixed pollutants system by any biological reactor operated in continuous mode. Furthermore, bromophenol along with chlorophenol and nitrophenol are usually the major constituents of paper pulp and pesticide industrial effluent. The present study investigated simultaneous biodegradation of these three pollutants with specially emphasis on substrate competition and crossed inhibition by Arthrobacter chlorophenolicus A6 in an upflow packed bed reactor (UPBR). A 2(3) full factorial design was employed with these pollutants at two different levels by varying their influent concentration in the range of 250-450 mg l(-1). Almost complete removal of all these pollutants and 97 % effluent toxicity removal were achieved in the UPBR at a pollutant loading rate of 1707 mg l(-1) day(-1) or lesser. However, at higher loading rates, the reactor performance deteriorated due to transient accumulation of toxic intermediates. Statistical analysis of the results revealed a strong negative interaction of 4-CP on 4-NP biodegradation. On the other hand, interaction effect between 4-CP and 4-BP was found to be insignificant. Among these three pollutants 4-NP preferentially degraded, however, 4-CP exerted more inhibitory effect on 4-NP biodegradation. This study demonstrated the potential of A. chlorophenolicus A6 for biodegradation of 4-BP in mixed pollutants system by a flow through UPBR system.

Hexavalent chromium [Cr(VI)] removal by the electrochemical ion-exchange process.

In the present investigation, the performance of a laboratory-scale plate and frame-type electrochemical ion-exchange (EIX) cell on removal ofhexavalent chromium from synthetic wastewater containing 5 mg/l of Cr(VI) was evaluated under varying applied voltages. Ruthenium dioxide-coated titanium plate (RuO2/Ti) was used as anode and stainless steel plates as cathode. The EIX cell was run at different hydraulic retention time (HRT). Before using in the electrochemical cell, the capacity of ion-exchange resin was evaluated through kinetic and isotherm equilibrium tests in batch mode. The batch kinetic study result showed that the equilibrium time for effective ion exchange with resin is 2 h. The isotherm equilibrium data fit well to both Freundlich and Langmuir isotherms. Maximum capacity (qm) of resin calculated from Langmuir isotherm was 71.42 mg/g. Up to 99% of chromium removal was noticed in the EIX cell containing fresh resin at applied voltages of 10 V and higher. Migration of chromium ion to anode chamber was not noticed while performing the experiment with fresh resin. As high as 50% removal of chromium was observed from the middle chamber containing exhausted resin at an applied voltage of 25 V when the influent flow rate was maintained at 45 min of HRT. The performance of the reactor was increased to 72% when the influent flow rate was decreased to maintain at 90 min of HRT. Build-up of chromium in the anode chamber took place when exhausted resin was used in the process.

Biological attenuation of arsenic and nitrate in a suspended growth denitrifying-sulphidogenic bioreactor and stability check of arsenic-laden biosolids.

Co-occurrence of arsenic and nitrate in groundwater sources at a wide range of concentrations is reported. In this work, performance of suspended growth semi-batch reactor was assessed for co-removal of arsenic and nitrate from simulated groundwater to meet the drinking water standards in the absence of iron. The bioreactor was inoculated with mixed bacterial culture and operated in the absence of oxygen for more than 450 days under varying influent arsenate (200-800 µg/L), nitrate concentrations (50-250 mg/L), and hydraulic retention time of 3-6 days. Complete nitrate removal was observed at all tested concentrations. Arsenic removal was found to meet drinking water standards from initial concentrations and up to 600 µg/L. The extended toxicity characteristic leaching procedure leaching experiments indicated that arsenic-laden biosolids would not constitute a hazardous waste. The arsenic leaching was found to increase with an increase in dissolved oxygen and the final leachate concentrations of arsenic were below 150 µg/L. The leaching experiments suggested maintaining non-alkaline conditions for minimum arsenic release from arsenic biosolids formed under sulphidogenic conditions. This study is the first to report that nitrate and arsenic can be simultaneously removed to meet drinking standards in a suspended growth bioreactor.

A practical approach on reuse of drinking water treatment plant residuals for fluoride removal.

The sustainable management of the voluminous waste from drinking water treatment plants has motivated environmental researchers towards several reuse options. Water treatment residues (WTR) are proven adsorbent for remediation of many water- and soil-borne anions (perchlorate, selenium and arsenic), and may be able to remove fluoride from contaminated water. In this study, the sustainable reuse of the freely available waste of the drinking water treatment plants, namely WTR, was explored for their fluoride removal potential to meet drinking water standards. WTR was characterized by specific surface area, Fourier transform infrared (FT-IR), scanning electron microscopy and X-ray powder diffraction (XRD). Batch adsorption experiments were conducted as a function of WTR dose, contact time, agitation speed, initial fluoride concentration, initial temperature and water pH to get best adsorption capacity. About 90% fluoride removal (from initial 5.0 mg/L) was observed within 2 h contact time at WTR dose of 28 g/L. Also, WTR effectively removed fluoride in the pH range of 5-8, whereas removal efficiency decreased at pH 9 or higher. The adsorption equilibrium was established within 120-150 min. Adsorption isotherm data were best fit to Langmuir (R 2 = 0.984) and Freundlich models (R 2 = 0.983), while adsorption kinetic study exhibited that second-order kinetic model was followed with rate constant of 0.038 g/mg min. The FT-IR and XRD analyses affirmed that the metal hydroxyl and metal oxide groups contributed to the fluoride removal. The experimental results show the promising potential of WTR as an adsorbent in fluoride removal from real contaminated groundwater.

Effects of backwashing strategy and dissolved oxygen on arsenic removal to meet drinking water standards in a sulfidogenic attached growth reactor.

Efficiency and feasibility of two backwashing methods (water-nitrogen and water-air assisted) on arsenic and its co-pollutants removal were assessed through running a sulfidogenic attached growth reactor (AGR) treating arsenic spiked simulated groundwater for about 600 days. Replacing water with nitrogen assisted backwashing (WNAB) by water with air assisted backwashing (WAAB) introduced dissolved oxygen (DO) as an additional electron acceptor, which required an increased empty bed contact time (EBCT) to retain the entire terminal electron accepting zones (DO, nitrate, arsenate and sulfate) within the reactor. Removal of arsenic to below 10 µg/L required a longer EBCT at higher influent DO in backwash water. Notably, MiSeq sequencing analysis confirmed the presence of diverse bacterial community on biofilm which can utilize multiple terminal electron acceptors present in the bioreactor.

Bio-attenuation of arsenic and iron coupled with nitrate remediation in multi-oxyanionic system: Batch and column studies.

Co-occurrence of arsenic and iron along with nitrate in groundwater makes the trio an onerous combination both in terms of potability and treatment. To meet drinking water guidelines, batch and column laboratory trials were conducted on simulated and bore-well water for attenuation of arsenic (1000 µg/L), iron (5 mg/L) and nitrate (150 mg/L). Increment in sulphate showed a direct individual impact on iron removal, meeting WHO guidelines. The bio-kinetic parameters were in the range of: µmax = 0.079-0.551/d, Ks = 116.18-645.19 mg/L, Kd = 0.0009-0.0077/d and Y = 0.034-0.094 mg MLVSS/mg COD. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) confirmed orpiment precipitation and/or co-precipitation with mackinawite are the key mechanisms for arsenic and iron attenuation. Column experiments were conducted by charging simulated groundwater containing arsenic (500 µg/L), nitrate (50 mg/L), sulphate (25 mg/L) and iron (3 mg/L) in an acetate (105 mg/L as COD) fed flow-through bioreactor at constant empty bed contact time of 60 min. Profile sampling illustrated segregation of different terminal electron accepting zones following thermodynamic yield for sequential removal of different oxyanions. This study showed the importance of considering microbially mediated terminal electron-accepting processes (TEAP) for multi-oxyanion removal in engineered systems.

Synthesis and characterization of carboxylic cation exchange bio-resin for heavy metal remediation.

A new carboxylic bio-resin was synthesized from raw arecanut husk through mercerization and ethylenediaminetetraacetic dianhydride (EDTAD) carboxylation. The synthesized bio-resin was characterized using thermogravimetric analysis, field emission scanning electron microscopy, proximate & ultimate analyses, mass percent gain/loss, potentiometric titrations, and Fourier transform infrared spectroscopy. Mercerization extracted lignin from the vesicles on the husk and EDTAD was ridged in to, through an acylation reaction in dimethylformamide media. The reaction induced carboxylic groups as high as 0.735mM/g and a cation exchange capacity of 2.01meq/g functionalized mercerized husk (FMH). Potentiometric titration data were fitted to a newly developed single-site proton adsorption model (PAM) that gave pKa of 3.29 and carboxylic groups concentration of 0.741mM/g. FMH showed 99% efficiency in Pb(II) removal from synthetic wastewater (initial concentration 0.157mM), for which the Pb(II) binding constant was 1.73×103L/mol as estimated from modified PAM. The exhaustion capacity was estimated to be 18.7mg/g of FMH. Desorption efficiency of Pb(II) from exhausted FMH was found to be about 97% with 0.1N HCl. The FMH simultaneously removed lead and cadmium below detection limit from a real lead acid battery wastewater along with the removal of Fe, Mg, Ni, and Co.

Investigation on stability and leaching characteristics of mixtures of biogenic arsenosulphides and iron sulphides formed under reduced conditions.

Arsenic is removed from aqueous phase through precipitation as arsenosulphides and/or co-precipitation and adsorption on iron sulphides. Studies were carried out to ascertain the stability of reduced biogenic arsenic and iron sulphide precipitates formed in an attached growth reactor (AGR) through a series of experiments based on Toxicity Characteristic Leaching Procedure (TCLP), aging and long term leaching tests. About half of the AGR was initially added with waste activated carbon (WAC) to support the growth of mixed microbial consortia and used for treatment of arsenic and iron contaminated simulated groundwater. The X-ray diffraction (XRD), X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy results indicated that the biosolids were mainly composed of arsenosulphides and iron sulphides. While TCLP and aging tests were conducted in anoxic as well as oxic conditions with the aim to evaluate stability of biomass containing biogenic sulphides, long term leaching test was conducted through supply of aerated distilled water to evaluate the stability of spent WAC as well. Results generated from the research indicate that the concentration of leached arsenic never exceeded 123 µg/L under all conditions tested, thus biosolids not imposing an environmental hazard.

Atrazine degradation in anaerobic environment by a mixed microbial consortium.

Atrazine degradation by anaerobic mixed culture microorganism in co-metabolic process and in absence of external carbon and nitrogen source was studied at influent atrazine concentration range of 0.5-15 mg/l. Wastewater of desired characteristic was prepared by the addition of various constituents in distilled water spiked with atrazine. In co-metabolic process, dextrose of various concentrations (150-2000 mg/l) was supplied as external carbon source. The reactors were operated in sequential batch mode in which 20% of treated effluent was replaced by the same amount of fresh wastewater everyday, thus maintaining a hydraulic retention time (HRT) equal to 5 days. In co-metabolic process, 40-50% of influent atrazine degradation was observed. First-order atrazine degradation rate (expressed in day(-1)) was better in co-metabolic process (5.5 x 10(-4)) than in absence of external carbon source (2.5 x 10(-5)) or carbon and nitrogen source (1.67 x 10(-5)). In presence of 2000 mg/l of dextrose, atrazine degradation was between 8% and 15% only. Maximum atrazine degradation was observed from wastewater containing 300 mg/l of dextrose and 5mg/l of atrazine. Influent atrazine concentration did not have much effect on the methanogenic bacteria which was clear from methane gas production and specific methanogenic activity (SMA).

Biodegradation of 4-bromophenol by Arthrobacter chlorophenolicus A6T in a newly designed packed bed reactor.

Bromophenol is listed as a priority pollutant by the U.S. EPA. However, there has been no report on the removal of bromophenol in any biological system that is operated in a continuous mode. The efficiency of Arthrobacter chlorophenolicus A6(T) on the biodegradation of 4-bromophenol (4-BP) in a newly designed packed bed reactor (PBR) was evaluated with different influent 4-BP concentrations between 400 mg l(-1) and 1200 mg l(-1) and hydraulic retention times (HRTs) between 24 h and 7.5 h. The response of the PBR to 4-BP shock loadings was also tested, and the bioreactor was found to adequately handle these shock loadings. The percentage of effluent toxicity in the PBR was tested using mixed microbial consortia as the test species; this experiment was performed using a 4-BP influent concentration of 1200 mg l(-1) and HRTs between 24 h and 7.5 h. A maximal 98% effluent toxicity removal was achieved when the PBR was operated at an HRT of 24 h. In the present study, 4-BP was used as the sole source of carbon and energy, and the complete removal of 4-BP was achieved with 4-BP loading rates of up to 2277 mg l(-1) day(-1).

Biodegradation of p-nitrophenol using Arthrobacter chlorophenolicus A6 in a novel upflow packed bed reactor.

A novel packed bed reactor (PBR) was designed with cross flow aeration at multiple ports along the depth to improve the hydrodynamic conditions of the reactor, and the biodegradation efficiency of Arthrobacter chlorophenolicus A6 on p-nitrophenol (PNP) removal in PBR at different PNP loading rates were evaluated. The novel PBR was designed to improve the hydrodynamic features such as mixing time profile (t(m95)), oxygen mass transfer coefficient (k(L)a), and overall gas hold up capacity (ɛ(G)) of the reactor. PNP concentration in the influent was varied between 600 and 1400 mg l(-1) whereas the hydraulic retention time (HRT) in the reactor was varied between 18 and 7.5h. Complete removal of PNP was achieved in the reactor up to a PNP loading rate of 2787 mg l(-1)d(-1). More than 99.9% removal of PNP was achieved in the reactor for an influent concentration of 1400 mg l(-1) and at 18 h HRT. In the present study, PNP was utilized as sole source of carbon and energy by A. chlorophenolicus A6. Furthermore, the bioreactor showed good compatibility in handling shock loading of PNP.

Hexavalent chromium [Cr(VI)] removal by acid modified waste activated carbons.

Fresh activated carbon (AC) and waste activated carbon (WAC) were pretreated by heating with mineral acids (sulfuric acid and nitric acid) at high temperature to prepare several grades of adsorbents to evaluate their performance on Cr(VI) removal from aqueous phase. Effects of temperature, agitation speed and pH were tested, and optimum conditions were evaluated. Kinetic study was performed under optimum conditions with several grades of modified adsorbents to know the rates of adsorption. Batch adsorption equilibrium data followed both, Freuindlich and Langmuir isotherms. Maximum adsorption capacity (q(max)) of the selected adsorbents treated with sulfuric acid (MWAC 1) and nitric acid (MWAC 2), calculated from Langmuir isotherm are 7.485 and 10.929 mg/g, respectively. Nitric acid treated adsorbent (MWAC 2) was used for column study to determine the constants of bed depth service time (BDST) model for adsorption column design.

Performance evaluation of waste activated carbon on atrazine removal from contaminated water.

In this study, the potential of spent activated carbon from water purifier (Aqua Guard, India) for the removal of atrazine (2 chloro-4 ethylamino-6-isopropylamino-1, 3, 5 triazine) from wastewaters was evaluated. Different grades of spent activated carbon were prepared by various pretreatments. Based on kinetic and equilibrium study results, spent activated carbon with a grain size of 0.3-0.5 mm and washed with distilled water (designated as WAC) was selected for fixed column studies. Batch adsorption equilibrium data followed both Freundlich and Langmuir isotherm. Fixed bed adsorption column with spent activated carbon as adsorbent was used as a polishing unit for the removal of atrazine from the effluent of an upflow anaerobic sludge blanket (UASB) reactor treating atrazine bearing domestic wastewater. Growth of bacteria on the surface of WAC was observed during column study and bacterial activity enhanced the effectiveness of adsorbent on atrazine removal from wastewater.

Performance of waste activated carbon as a low-cost adsorbent for the removal of anionic surfactant from aquatic environment.

In the present study, different low cost adsorbents were screened for their sodium dodecyl sulfate (SDS, an anionic surfactant) removal capacity. Waste activated carbon (WAC) from the aqua purifier has shown high efficiency for SDS removal. The performance evaluation in the presence of various ions (Ca2+, SO4(2-), NO3-, and Cl-) and at various pH was studied. Desorption studies were conducted using simple sonication and pH variation technique. Column adsorption studies were performed. SEM and EDS studies were done on the adsorbing material before adsorption, after adsorption and after desorption of SDS.