Electrochemical oxidation of Florfenicol in aqueous solution with mixed metal oxide electrode: Operational factors, reaction by-products and toxicity evaluation.

Veterinary antibiotics have become an emerging pollutant in water and wastewater sources due to excess usage, toxicity and resistance to traditional water and wastewater treatment. The present study explored the degradation of a model antibiotic- Florfenicol (FF) using electrochemical oxidation (EO) with Ti-RuO2/IrO2 anode. The anode material was characterized using SEM-EDS studies expressing stable structure and optimal interaction of the neighboring metal oxides with each other. The EDS results showed the presence of Ru, Ir, Ti, O and C elements with 6.44%, 2.57%, 9.61%, 52.74% and 28.64% atomic weight percentages, respectively. Optimization studies revealed pH 5, 30 mA cm-2 current density and 0.05 M Na2SO4 for 5 mg L-1 FF achieved 90% TOC removal within 360 min treatment time. The degradation followed pseudo-first order kinetics. LC-Q-TOF-MS studies revealed six predominant byproducts illustrating hydroxylation, deflourination, and dechlorination to be the major degradation mechanisms during the electrochemical oxidation of FF. Ion chromatography studies revealed an increase in Cl-, F- and NO3- ions as treatment time progressed with Cl- decreasing after the initial phase of the treatment. Toxicity studies using Zebrafish (Danio rerio) embryo showed the treated sample to be toxic inducing developmental disorders such as pericardial edema, yolk sac edema, spinal curvature and tail malformation at 96 h post fertilization (hpf). Compared to control, delayed hatching and coagulation were observed in treated embryos. Overall, this study sets the stage for understanding the effect of mixed metal oxide (MMO) anodes on the degradation of veterinary antibiotic-polluted water and wastewater sources using electrochemical oxidation.

Residential houses - a major point source of microplastic pollution: insights on the various sources, their transport, transformation, and toxicity behaviour.

Municipal wastewater has been considered as one of the largest contributors and carriers of microplastics to the aquatic environment. However, the various residential activities that generate municipal wastewater are equally significant whenever the source of microplastics in aquatic system is accounted. However, so far, only municipal wastewater has received wide attention in previous review articles. Hence, this review article is written to address this gap by highlighting, firstly, the chances of microplastics arising from the usage of personal care products (PCPs), laundry washing, face masks, and other potential sources. Thereafter, the various factors influencing the generation and intensity of indoor microplastic pollution and the evidence available on the possibility of microplastic inhalation by humans and pet animals are explained. Followed by that, the removal efficiency of microplastics observed in wastewater treatment plants, the fate of microplastics present in the effluent and biosolids, and their impact on aquatic and soil environment are explored. Furthermore, the impact of aging on the characteristics of microsized plastics has been explored. Finally, the influence of age and size of microplastics on the toxicity effects and the factors impacting the retention and accumulation of microplastics in aquatic species are reviewed. Furthermore, the prominent pathway of microplastics into the human body and the studies available on the toxicity effects observed in human cells upon exposure to microplastics of different characteristics are explored.

EfectroH2O: Development and evaluation of a novel treatment technology for high-brine industrial wastewater.

Textile production is one of the main sources of freshwater consumption by industries worldwide. In addition, according to the world bank, 20 % of the wastewater generated globally is caused by textile wet-processing. Textile wet-processing includes the processes in textile production where garments are dyed or given the final functions like water-repellency. Several thousand chemicals were used in this process, some of which are highly toxic. Discharging untreated or insufficiently treated wastewater in water bodies results in high pollution levels, severely impacting the environment and human health. Especially in textile-producing countries like India, environmental pollution and water consumption from textile wet-processing have severe impacts. Next to the high volume of chemicals used in textile production, the high salt concentration in textile wastewater also poses a challenge and is critical for freshwater systems. Moreover, textile wastewater is one of the most difficult to treat wastewater. Currently, used treatment technologies do not meet the requirements to treat textile wastewater. Therefore, the further development of efficient treatment technologies for textile wastewater is critically important. Hence, in the interdisciplinary project, effect-based monitoring demonstrates the efficiency of electrically-driven water treatment processes to remove salts and micropollutants from process water (EfectroH2O), a low-energy Zero Liquid Discharge (ZLD) textile wastewater treatment technology is being developed consisting of a combination of capacitive deionization (CDI) and advanced oxidation processes (AOP). In addition to treatment technology development, methods for evaluating the efficiency of treatment technologies also need to be improved. Currently, mainly physicochemical parameters such as pH, biochemical oxygen demand (BOD) and chemical oxygen demand (COD) are tested worldwide to check water quality. However, these methods are insufficient to make a statement about the toxic potential of such complex mixtures as textile wastewater. Therefore, also next to chemical analyses, effect-based methods (EBM) are used to verify the treated wastewater.

Distribution of microplastics in the catchment region of Pallikaranai marshland, a Ramsar site in Chennai, India.

Microplastics are persistent toxic pollutants, detected in different environmental compartments. Numerous studies on the characteristics and distribution of microplastics present in different environmental matrices are being carried out. However, limited studies have been performed in environmental systems like eco-sensitive freshwater marshlands. Therefore, to enrich the existing knowledge and understanding, this current study has analysed the distribution and characteristics of microplastics present in the catchment region of Pallikaranai marshland, Chennai, India. Both surface water and sediment samples were contaminated with microplastics in the range of 740-2826 items/m3and 700 to 5833 items/kg of dry sediment, respectively. Compared to other shapes, fibrous microplastics were predominant in most of the surface water (n = 11) and sediment (n = 8) samples. The abundant presence of smaller microplastics (<1 mm) in the surface water suggests elevated impacts on the aquatic species owing to their higher bioavailability. Elevated anthropogenic activities and frequent movement of people in urban and residential areas were noted to possibly influence the spatial distribution of microplastics. Furthermore, heavy metals' occurrence on microplastics was investigated using X-Ray Fluorescence Analyser (XRF) and Zn, Fe, Ti, and Ni are the commonly detected (>50% of the samples) elements. The estimated average pollution load index of 2.5 indicates the polluted state of Pallikaranai catchment region.

Demonstrating a Comprehensive Wastewater-Based Surveillance Approach That Differentiates Globally Sourced Resistomes.

Wastewater-based surveillance (WBS) for disease monitoring is highly promising but requires consistent methodologies that incorporate predetermined objectives, targets, and metrics. Herein, we describe a comprehensive metagenomics-based approach for global surveillance of antibiotic resistance in sewage that enables assessment of 1) which antibiotic resistance genes (ARGs) are shared across regions/communities; 2) which ARGs are discriminatory; and 3) factors associated with overall trends in ARGs, such as antibiotic concentrations. Across an internationally sourced transect of sewage samples collected using a centralized, standardized protocol, ARG relative abundances (16S rRNA gene-normalized) were highest in Hong Kong and India and lowest in Sweden and Switzerland, reflecting national policy, measured antibiotic concentrations, and metal resistance genes. Asian versus European/US resistomes were distinct, with macrolide-lincosamide-streptogramin, phenicol, quinolone, and tetracycline versus multidrug resistance ARGs being discriminatory, respectively. Regional trends in measured antibiotic concentrations differed from trends expected from public sales data. This could reflect unaccounted uses, captured only by the WBS approach. If properly benchmarked, antibiotic WBS might complement public sales and consumption statistics in the future. The WBS approach defined herein demonstrates multisite comparability and sensitivity to local/regional factors.

Inactivation behavior and intracellular changes in Escherichia coli during electro-oxidation process using Ti/Sb-SnO2/PbO2 anode: Elucidation of the disinfection mechanism.

This study investigates the behavior and intracellular changes in Escherichia coli (model organism) during electro-oxidation with Ti/Sb-SnO2/PbO2 anode in a chlorine free electrochemical system. Preliminary studies were conducted to understand the effect of initial E. coli concentration and applied current density on disinfection. At an applied current density 30 mA cm-2, 7 log reduction of E. coli was achieved in 75 min. The role of reactive oxygen species' (ROS) in E.coli disinfection was evaluated, which confirmed hydroxyl (•OH) radical as the predominant ROS in electro-oxidation. Observations were carried out at cell and molecular level to understand E.coli inactivation mechanism. Scanning electron microscopy images confirmed oxidative damage of the cell wall and irreversible cell death. Intracellular and extracellular protein quantification and genetic material release further confirmed cell component leakage due to cell wall rupture and degradation due to •OH radical interaction. Change in cell membrane potential suggests the colloidal nature of E. coli cells under applied current density. Plasmid deoxyribonucleic acid degradation study confirmed fragmentation and degradation of released genetic material. Overall, effective disinfection could be achieved by electro-oxidation, which ensures effective inactivation and prevents regrowth of E. coli. Disinfection of real wastewater was achieved in 12 min at an applied current density 30 mA cm-2. Real wastewater study further confirmed that effective disinfection is possible with a low cost electrode material such as Ti/Sb-SnO2/PbO2. Energy consumed during disinfection was determined to be 4.978 kWh m-3 for real wastewater disinfection at applied current density 30 mA cm-2. Cost of operation was estimated and stability of the electrode was studied to evaluate the feasibility of large scale operation. Relatively low energy and less disinfection time makes this technology suitable for field scale applications.

Tubular Sediment-Water Electrolytic Fuel Cell for Dual-Phase Hexavalent Chromium Reduction.

A novel tubular sediment-water electrolytic fuel cell (SWEFC) was fabricated for the reduction of Cr(VI) in a dual-phase system. The approach simulates a standing water body with Cr(VI)-contaminated overlying water (electrolyte) and bottom sediment phase with electrodes placed in both the phases, supplemented with urea as a potential electron donor. Cr(VI) reduction efficiency of 93.2 ± 1.3% from electrolyte (in 1.5 h) and 81.2 ± 1.3% from the sediment phase (in 8 h) with an initial Cr(VI) concentration of 1,000 mg/L was observed in a single-cell configuration. The effect of initial Cr(VI) concentration, variation in sediment salinity and pH, and different electron donors on the SWEFC performance were systematically investigated. SWEFC showed enhanced performance with 2.4-fold higher current (193.9 mA) at 400 mg/L Cr(VI) concentration when cow dung was used as a low-cost alternative to urea as an electron donor. Furthermore, reactor scalability studies were carried out with nine-anode and nine-cathode configuration (3 L electrolyte and 2 kg sediment), and reduction efficiencies of 98.9 ± 0.9% (in 1 h) and 97.6 ± 2.2% (in 8 h) were observed from the electrolyte and sediment phases, respectively. The proposed sediment-water electrolytic fuel cell can be an advanced and environmentally benign strategy for Cr(VI) remediation from contaminated sediment-water interfaces along with electricity generation.

Deterministic and probabilistic health risk assessment for exposure to non-steroidal anti-inflammatory drugs in an Indian river.

This study presents deterministic and probabilistic human health risk assessment using Monte Carlo simulations on exposure to an Indian river, Kaveri, which has been contaminated by non-steroidal anti-inflammatory drugs (NSAIDs). The NSAIDs of concern are naproxen, ibuprofen, aspirin, ketoprofen, and diclofenac. We have considered three exposure scenarios (water ingestion, dermal exposure, and fish ingestion) for four different age groups (0-5, 6-10, 11-18, and 19-70 years). Deterministic risk assessment revealed teenagers to be the most sensitive receptors and water ingestion to be the most crucial pathway contributing to maximum health risk (79 to 86%). Based on the results of Monte Carlo simulations, it was found that the probability of exceeding the deterministic mean risks ranged from 17 to 39% for different exposure routes. High end risk estimates such as 95th percentiles and maximum values of HQ for the entire population did not exceed the USEPA allowable risk. This implies that the NSAIDs at the detected concentrations in the Kaveri river may not pose adverse health effects even in the worst-case scenario. Among the five NSAIDs, diclofenac was found to be the major contributor for health risk. Moreover, the concentration of diclofenac was just one order less than the estimated site-specific threshold concentrations. From sensitivity analysis, the most and the least impactful parameters were found to be water ingestion rate and fish ingestion rate respectively.

Human health risk assessment for exposure to BTEXN in an urban aquifer using deterministic and probabilistic methods: A case study of Chennai city, India.

The aquifer in Tondiarpet, Chennai, had been severely contaminated with petroleum fuels due to an underground pipeline leakage. Groundwater samples were analyzed quarterly for priority pollutants such as benzene, toluene, ethylbenzene, xylenes, and naphthalene (BTEXN) using purge and trap gas chromatography and mass spectrometer from 2016 to 2018. The maximum concentrations of BTEXN in groundwater at the site were found to be greater than the permissible limits significantly. Among the five sampling locations (MW1, MW2, MW3, MW4, and MW5), mean BTEXN levels were found to be higher near MW2, confirming the source location of petroleum leakage. Human health risk assessment was carried out using deterministic and probabilistic methods for exposure to BTEXN by oral and dermal exposure pathways. Risk analysis indicated that mean cancer and non-cancer risks were many times higher than the allowable limits of 1E-06 and 1 respectively in all age groups (children, teens, and adults), implying the adverse health effects. Oral exposure is predominately contributing (60-80%) to the total health risk in comparison to the dermal exposure route. Variability and uncertainty were addressed using the Monte Carlo simulations and the resultant minimum, maximum, 5th, 95th, and mean percentile risks were predicted. Under the random exposure conditions to BTEXN, it was estimated that the risk would become unacceptable for >98.7% of the exposed population. Based on the sensitivity analysis, exposure duration, and ingestion rate are the crucial variables contributing significantly to the health risk. As part of the risk management, preliminary remediation goals for the study site were estimated, which require >99% removal of the BTEXN contamination for risk-free exposures. It is suggested that the residents of Tondiarpet shouldn't utilize the contaminated groundwater mainly for oral ingestion to lower the cancer incidence related to exposure to BTEXN.

Comprehensive treatment of urban wastewaters using electrochemical advanced oxidation process.

This study mainly focuses on the efficiency of anodic oxidation process (Ti/Sb-SnO2/PbO2 as anode and stainless steel as the cathode) in treating two different streams of urban wastewater, one from the influent of sequence batch reactor (WW1) and other from the effluent of constructed wetland (WW2). The effect of different operational parameters such as current density, hydraulic retention time, exposed electrode surface area, phosphorous, ammonia-nitrogen, nitrates, and coliform bacteria was studied. For an optimized current density of 30 mA/cm2 and an electrode surface area of 30 cm2, almost complete removal of COD and ammonia-nitrogen were achieved with both wastewaters (WW1 & WW2), while in case of phosphorous, 50% and 98% removal efficiencies were observed. Electrode deposition was analyzed using SEM-EDS and XRD, which confirms the presence of calcium and magnesium phosphates on the surface on the anode, which attributes to the phosphate removal. Electrochemical disinfection studies showed that complete inactivation of bacteria takes place within 30 min for WW1 and 60 min for WW2, and the cell morphological changes were studied using SEM analysis. Degradation of different micropollutants present in the wastewaters was evaluated with the aid of GC-MS. ICP - MS analysis confirmed that there was no leaching of lead from the anode surface, and the lead which is already present in the wastewater gets reduced to a permissible level, which further increases the treatment efficiency. Hence cleaner and comprehensive treatment of real urban wastewaters through anodic oxidation process was successfully demonstrated in this work.

Single-step removal of Hexavalent chromium and phenol using meso zerovalent iron.

Novel meso-zero valent iron (mZVI) was investigated for treating complex wastewater containing toxic heavy metal Cr6+ and organic compound phenol. This study is first of its kind illustrating coupled removal in single-step with H2O2 playing a major role as an oxidant and reductant. The mechanism involved was electron transfer from Fe0/2+ to Cr6+ resulting in Fe2+/3+ which in turn was consumed for phenol oxidation returning as Fe2+ into the system for further Cr6+ reduction. While comparing, single-step simultaneous removal of Cr6+ and phenol showed better performance in terms of pollutant removal, Fe2+/3+ recurrent reaction and precipitation generation, double-tep sequential removal performed better in iron active-corrosion time. It was also observed that the entire redox cycle of Cr6+-Cr3+-Cr6+ was reusable for co-contaminant phenol degradation at all pH with the recurrence of Fe2+-Fe3+-Fe2+. The proposed technique was checked for its viability in a single batch reactor and the complex chemistry of the reactions are unfolded by conducting chemical speciation and mass balance study at every stage of reaction. The unique functioning of mZVI was proven with micro-analysis of ZVI's surface and compared with granular ZVI, cZVI. The results obtained from this study open the door for a safer and cleaner single treatment system in removing both toxic heavy metals and organic compounds from contaminated surface water, groundwater and many such industrial effluents.

Liquid crystal display electrode-assisted bio-electroperoxone treatment train for the abatement of organic contaminants in a pharmaceutical wastewater.

Pharmaceutical contaminants present in wastewaters cause severe health hazards among chronically exposed population. Emerging pharmaceutically active contaminants pose a serious challenge to conventional treatment technologies. Employing advanced treatment technologies for the abatement of such contaminants is usually energy-intensive. In this study, a complex pharmaceutical wastewater from a pharmaceutical industry in California, USA, was treated by employing a novel bio-electrochemical treatment train system. Labeled "Bio-electroperoxone," our proposed system comprises (i) an electrically bound biofilm reactor (EBBR) that accelerates bacterial adhesion for the removal of biodegradable and persistent organics and (ii) an electroperoxone reactor that removes recalcitrant organics with minimal energy uptake. The EBBR comprises a platinum-coated titanium cathode and a conductive nematic liquid crystal display electrode (NLCE) obtained from electronic waste that serves as the anode. Characterization of functional groups, morphology, and elemental mapping of NLCE were carried out to explain mechanisms for rapid biofilm attachment. The concomitant electroperoxone reactor comprises a platinum-coated titanium (Pt-Ti) anode and a reticulated vitreous carbon (RVC) cathode that catalyzes the two-electron reduction of oxygen to form in situ H2O2. The bio-electroperoxone system (i) inactivated 99.99% of the micro-organisms, removed (ii) 92.20% of the color, (iii) 84.72% of the total suspended solids, and (iv) 89% of the total organic carbon (TOC). Possible mechanisms for the degradation of organic contaminants are elucidated. Bio-electroperoxone thus paves the way for an efficient and sustainable approach for the efficient removal of both biodegradable and recalcitrant, persistent organic contaminants from pharmaceutical and possibly other complex wastewaters.

Environmental burden by an open dumpsite in urban India.

Open municipal solid waste (MSW) dumpsites are nowadays looming hotspots for water, air, and land pollution. Fresh and old MSW samples collected from a dumpsite in the coastal city of India were analyzed for moisture content, volatile content, energy content, elements, and toxic heavy metals. The compositional analysis results showed that fresh MSW consisted of 36% by weight bio-waste (food waste, yard waste, coconut waste) and around 30% recyclable materials (plastics, paper, cardboard, and metals). Approximately, 62% of the total fresh MSW was found to be combustible materials (plastics, paper, textile, rubber, cardboard, yard waste, and coconut husks). The analysis of old MSW samples collected from different depths (3-4 m and 6-7 m) showed the dominance of plastics (25-33%) and mixed residue (28-55%) having high energy content. Measurements of gaseous emission below 6-7 m from the surface indicated a higher concentration of methane (CH4:5.85 ±â€¯0.12%) and lower concentration of carbon monoxide (CO: 3.82 ±â€¯1.3 ppm), and hydrogen sulfide (H2S:10.15 ±â€¯2.2 ppm). Haphazard dumping, waste characteristics, waste pile compaction processes and heat propagation due to deliberate fire may stimulate spontaneous fires.

Microwave (MW) remediation of hydrocarbon contaminated soil using spent graphite - An approach for waste as a resource.

In this study, we have explored the possibility of using an industrial waste for remediation of heavy fuel oil contaminated soil. Microwave (MW) heating in the presence of spent graphite (SG) from an auto forging industry has been used for the remediation. The physico-chemical characterization of SG and contaminated soil were done. Microwave remediation experiments were conducted in a lab scale unit and the effect of different parameters like microwave power, susceptor loading and treatment time were studied and optimized. The contaminated and decontaminated soils were analysed using GC-MS for total petroleum hydrocarbons (TPH), Total Organic Carbon and CHNS analyzers. Batch experiments of soil remediation showed that the TPH removal efficiencies (%) of 41.25, 87.77 and 91.18 at 300, 450 and 600 W respectively at SG concentration of 2.5 (wt. %) for a reaction time of 60 min. The addition of SG as susceptor enhanced the desorption of long chain hydrocarbons (C12-C29) present in the soil. Desorption of hydrocarbons from the soil fits well with first order kinetic model. This study successfully demonstrated the reuse of spent graphite (a lubricant waste) recovered from metal forging operations for remediating the fuel oil contaminated soil.

Implementation of Solute Transport in the Vadose Zone into the "HYDRUS Package for MODFLOW".

The "HYDRUS package for MODFLOW" is an existing MODFLOW package that allows MODFLOW to simultaneously evaluate transient water flow in both unsaturated and saturated zones. The package is based on incorporating parts of the HYDRUS-1D model (to simulate unsaturated water flow in the vadose zone) into MODFLOW (to simulate saturated groundwater flow). The coupled model is effective in addressing spatially variable saturated-unsaturated hydrological processes at the regional scale. However, one of the major limitations of this coupled model is that it does not have the capability to simulate solute transport along with water flow and therefore, the model cannot be employed for evaluating groundwater contamination. In this work, a modified unsaturated flow and transport package (modified HYDRUS package for MODFLOW and MT3DMS) has been developed and linked to the three-dimensional (3D) groundwater flow model MODFLOW and the 3D groundwater solute transport model MT3DMS. The new package can simulate, in addition to water flow in the vadose zone, also solute transport involving many biogeochemical processes and reactions, including first-order degradation, volatilization, linear or nonlinear sorption, one-site kinetic sorption, two-site sorption, and two-kinetic sites sorption. Due to complex interactions at the groundwater table, certain modifications of the pressure head (compared to the original coupling) and solute concentration profiles were incorporated into the modified HYDRUS package. The performance of the newly developed model is evaluated using HYDRUS (2D/3D), and the results indicate that the new model is effective in simulating the movement of water and contaminants in the saturated-unsaturated flow domains.

Hexavalent chromium reduction through redox electrolytic cell with urea and cow urine as anolyte.

The present study demonstrates the potential utilization of urea/cow urine as anolyte for Cr(VI) reduction via a simple three-chambered electrolytic cell. The inherent chemical energy in the dual-waste stream (Cr(VI)-urea/urine) is employed for its self-oxidation-reduction without the need for any external energy supply. Ni foam as electroactive anode and catalyst-free carbon felt as cathode, along with the appropriate positioning of ion-selective separators, indirectly improved the cell performance by impeding electrolyte crossover. A fundamental study involving five different membrane configurations was conducted herein to improve Cr(VI) reduction efficiency. The Cr(VI) reduction efficiencies were 11.84 ±â€¯0.27%, 10.55 ±â€¯0.17%, 77.24 ±â€¯0.38% at 24 h, 13.57 ±â€¯0.25% at 72 h with glass frit, cation exchange membrane (CEM), sandwiched membrane, and anion exchange membrane (AEM) as separators in a dual-chambered H-cell, respectively, with an initial Cr(VI) concentration of 100 mg/L. The fifth configuration, consisting of a middle chamber between the anode and cathode with the CEM close to the anode and the AEM close to the cathode resulted in a reduction efficiency of 79.98 ±â€¯2.24% within 45 min for an initial Cr(VI) concentration of 400 mg/L. The first order rate constants were determined to be 0.024, 0.018, and 0.013 min-1 for Cr(VI) concentrations of 100, 200, and 400 mg/L, respectively. Moreover, when urea was replaced with cow urine as anolyte, a reduction efficiency of 98.94 ±â€¯1.28% was achieved at pH 2 in 45 min with 400 mg/L as initial Cr(VI) concentration. Furthermore, the XPS spectra of reduced Cr corresponding to binding energies of 579.4 eV and 589.3 eV, respectively, confirmed the presence of low-toxic Cr(III). The effect of applied load, initial Cr(VI) and urea concentration, Cr(VI) reduction under different initial H2SO4 concentrations were succinctly investigated to evaluate the performance of the electrolytic cell. The redox electrolytic cell can thus be an alternative to the conventional chemical or energy intensive processes for the reduction of hexavalent chromium.

Environmental impacts of the Chennai oil spill accident - A case study.

Chennai, a coastal city in India with a population of over 7 million people, was impacted by a major oil spill on January 28th 2017. The spill occurred when two cargo ships collided about two miles away from the Chennai shoreline. The accident released about 75 metric tons of heavy fuel oil into the Bay of Bengal. This case study provides field observations and laboratory characterization data for this oil spill accident. Our field observations show that the seawalls and groins, which were installed along the Chennai shoreline to manage coastal erosion problems, played a significant role in controlling the oil deposition patterns. A large amount of oil was trapped within the relatively stagnant zone near the seawall-groin intersection region. The initial cleanup efforts used manual methods to skim the trapped oil and these efforts indeed helped recover large amount of oil. Our laboratory data show that the Chennai oil spill residues have unique fingerprints of hopanes and steranes which can be used to track the spill. Our weathering experiments show that volatilization processes should have played a significant role in degrading the oil during initial hours. The characterization data show that the source oil contained about 503,000 mg/kg of total petroleum hydrocarbons (TPH) and 17,586 mg/kg of total polycyclic aromatic hydrocarbons (PAHs). The field samples collected 6 and 62 days after the spill contained about 71,000 and 28,000 mg/kg of TPH and 4854 and 4016 mg/kg of total PAHs, respectively. The field samples had a relatively large percentage of heavy PAHs, and most of these PAHs are highly toxic compounds that are difficult to weather and their long-term effects on coastal ecosystems are largely unknown. Therefore, more detailed studies are needed to monitor and track the long term environmental impacts of the Chennai oil spill residues on the Bay of Bengal coastal ecosystem.

Human health risk assessment of ground water contaminated with petroleum PAHs using Monte Carlo simulations: A case study of an Indian metropolitan city.

Underground pipelines are frequently used to transport petroleum fuels, through industrial as well as residential zones. Chennai is one of the four largest metropolitan cities of India. The region of interest in this study is located in the northern part of the Chennai. Ground water of this area was contaminated with polyaromatic hydrocarbons (PAHs) from the leaking oil storage tanks and pipe lines. Health risk assessment was conducted for exposure to PAHs in the ground water using incremental life time cancer risk (ILCR) models coupled with benzo[a]pyrene toxic equivalent method. The exposure pathways considered in this study were direct water ingestion and dermal contact under residential scenario. Exposure input parameters were transformed to statistical parameters using lognormal/uniform distributions and resultant probabilities of cancer risk were estimated by performing Monte Carlo simulations. Preliminary remediation goals were predicted using the combination of the cancer risk models of all the exposure routes with the consideration of high-safety risk of 1-in-1 million. Results showed that the cancer risk is predominantly contributed (greater than 98%) by dermal exposure than the oral in both adults and children. The total ILCR is found to be greater than a low safety risk of 1-in-10,000 with higher probability percentages (>90%). The 95th percentile values of the risk were presented in order to address the need for remediation. Appropriate remedial and treatment methods for the subject site were proposed. The results of the study will be useful for the regulatory boards and policy makers in India in understanding the actual impact of the contamination on receptors, setting up final remediation goals and deciding on a specific remedial method.

Understanding the hydrologic control of N cycle: Effect of water filled pore space on heterotrophic nitrification, denitrification and dissimilatory nitrate reduction to ammonium mechanisms in unsaturated soils.

Irrigation practice will be effective if it supplies optimal water and nutrients to crops and act as a filter for contaminants leaching to ground water. There is always a scope for improving the fertilizer use efficiency and scheduling of wastewater irrigation if the fate and transport of nutrients particularly nitrogenous compounds in the soil are well understood. In the present study, nitrogen transport experiments for two different agricultural soils are performed under varying saturation 33, 57, 78% water filled pore space for sandy soil 1 and 52, 81 and 96% for loam soil 2. A HYDRUS 2D model with constructed wetland (CW2D) module could simulate aerobic nitrification and anoxic denitrification well for both soils and estimated the reaction kinetics. A hot spot of Dissimilatory Nitrate Reduction to Ammonium (DNRA) pathway has been observed at 81% moisture content for a loamy sand soil. The presence of high organic content and reductive soil environment (5.53 C/NO3- ratio; ORP=-125mV) results in ammonium accumulation of 16.85mg in the soil. The overall observation from this study is nitrification occurs in a wide range of saturations 33-78% with highest at 57% whereas denitrification is significant at higher water saturations 57-78% for sandy soil texture. For a loamy sand soil, denitrification is dominant at 96% saturation with least nitrification at all saturation studies. The greatest nitrogen losses (>90%) was observed for soil 2 while 30-70% for soil1. The slow dispersive subsurface transport with varying oxygen dynamics enhanced nitrogen losses from soil2 due to lesser soil permeability. This in turn, prevents NO3- leaching and groundwater contamination. This type of modeling study should be used before planning field experiments for designing optimal irrigation and fertigation schedules.

An assessment of subsurface contamination of an urban coastal aquifer due to oil spill.

Incidences of leakages of chemicals from underground oil storage tanks or oil-carrying pipelines have posed huge threat to the coastal aquifers around the world. One such leak was recently identified and notified by the people of Tondiarpet, Chennai, India. The assessment of the contamination level was done by obtaining electrical resistivity maps of the subsurface, drilling of 20 new borewells for soil and water analysis, and testing the water quality of 30 existing borewells. Samples were collected from the borewells, and observations were made that included parameters such as odor, moisture, contamination characteristics, lithology, groundwater level, thickness of the free product that are used to demarcate the extent of soil, and water contamination. Furthermore, a multigas detector was used to detect hydrocarbon presence as soil vapor. Moreover, to capture the transport of dissolved hydrocarbons, 10 samples were collected in the periphery of the study area and were analyzed for the presence of petroleum hydrocarbon and polyaromatic hydrocarbon. Analysis of the data indicated the presence of free-phase hydrocarbon in soil and groundwater close to the junction of Thiruvottiyur high (TH) road (TH) and Varadaja Perumal Koil (VPK) street. Although the contaminant plume is confined to a limited area, it has spread more to the southern and eastern side of the pipeline possibly due to continuous abstraction of groundwater by residential apartments. After cutting a trench along the VPK street and plotting of the plume delineation map, observations indicated that the source of the hydrocarbon leak is present in VPK street close to TH road. A multipronged strategy was suggested targeting the remediation of oil in various phases.