Migration of Plasticizers from Polyethylene Terephthalate and Low-Density Polyethylene Casing into Bottled Water: A Case Study From India.

Mineral bottled water packed in three polymers viz., virgin polyethylene terephthalate (PET), recycled PET, and low-density polyethylene (LDPE) were investigated for the occurrence, migration, and health risk of phthalic acid esters (PAEs) at 25 °C, 35 °C, and 45 °C. The average concentration of six USEPA priority PAEs in refrigerated water samples was highest in recycled PET> LDPE > virgin PET. The highest leaching was seen at 45 °C after 2 days for LDPE water packets with ∑6PAEs amounting to 64,300 ng/L. Similarly, for recycled PET, the highest migration was seen at 45 °C after seven days (3,800 µg/L). Bis 2-ethyl hexyl phthalate (DEHP) and di-n-butyl phthalate (DnBP) were the predominant plasticizers from PET bottles and LDPE water packets, respectively. Predicted concentration after three weeks based on best fit obtained through the polynomial model for PET bottles was seen higher than the recommended limit suggested by USEPA (6 µg/L) and WHO (8 µg/L).

Investigation of distribution, sources and flux of perfluorinated compounds in major southern Indian rivers and their risk assessment.

Perfluorinated compounds (PFCs) are a group of emerging contaminants still less reported in rivers, particularly southern India. Therefore, we investigated the fate of 13 PFCs in three major rivers in southern India during post-monsoon and summer seasons. Twelve PFCs were detected, with an average total PFCs of 1853 ± 1463 pg/l. However, the total PFCs recorded in ppost-monsoon and summer seasons ranged from ND (none detected) to 10,545 pg/l and ND to 4960 pg/l, respectively. Among the individual congeners, perfluoro-n-hexanoic acid (PFHxA) had the highest detection average (929 ± 710 pg/l). The higher detection of short chain PFCs signifies their increasing wide usage as an alternative to perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Higher levels of PFCs were observed in summer than post-monsoon season in the river Kaveri, which is mainly attributed to the decrease in river flow. A multidimensional source identification revealed domestic and commercial wastewater as the major source. A correlation analysis showed that most of the detected PFCs share the common source and undergo co-migration into rivers. The flux of PFCs into the Bay of Bengal, loaded by the Kaveri (15 kg/yr) and the Tamiraparani (2.2 kg/yr) rivers, signifies lower per capita emissions than other rivers in India and other countries. Further, the PFC levels found in the rivers can be considered safe for human consumption and aquatic organisms based on international guidelines. Being the first hand report in southern Indian rivers, the results warrant further investigation to understand the exact sources, fate and removal in detail.

Plasticizers and bisphenol A in Adyar and Cooum riverine sediments, India: occurrences, sources and risk assessment.

Adyar and Cooum, the two rivers intersecting Chennai city, are exposed to serious pollution due to the release of large quantities of dumped waste, untreated wastewater and sewage. Sediments can act as repository for emerging organic contaminants. Hence, we have monitored the occurrence and risk associated with plasticizers [six phthalic acid esters (PAEs), bis(2-ethyl hexyl adipate) (DEHA)] and bisphenol A (BPA) in surface riverine sediments of Adyar and Cooum rivers from residential/commercial, industrial and electronic waste recycling sites. Σ7plasticizers (PAEs + DEHA) in the Adyar riverine sediment (ARS) and Cooum riverine sediment (CRS) varied between 51.82-1796 and 28.13-856 ng/g, respectively. More than three-fourth of Σ7plasticizers came from bis(2-ethylhexyl) phthalate (DEHP), in accordance with the high production and usage of this compound. BPA varied between 10.70-2026 and 7.58-1398 ng/g in ARS and CRS, respectively. Average concentrations of plasticizers and BPA were four times higher in electronic waste (e-waste) recycling sites when compared with industrial and residential/commercial sites. BPA and DEHP showed a strong and significant correlation (R2 = 0.7; p < 0.01) in the e-waste sites thereby indicating common source types. Sites present at close proximity to raw sewage pumping stations contributed to 70% of the total BPA observed in this study. For the derived pore water concentration of plasticizers and BPA, the ecotoxicological risk has been found to be higher in ARS over CRS. However, sediment concentrations in all the sites of ARS and CRS were much below the recommended serious risk concentration for human (SRChuman) and serious risk concentration for ecotoxicological (SRCeco).

Occurrence of polycyclic aromatic hydrocarbons (PAHs) in air and soil surrounding a coal-fired thermal power plant in the south-west coast of India.

This investigation focused on the potential sources of polycyclic aromatic hydrocarbons (PAHs) in different matrices and their temporal variations surrounding a coal-fired thermal power plant in India. Samples were collected in different seasons for 1 year. Gas chromatography-mass spectroscopy (GC-MS) was used to perform the measurement of 16 priority PAHs. Average PAH concentrations were ranged from 0.71 to 2.99 ng/m3 in air and 1.59-22.7 ng/g in soil respectively. High levels of PAHs were found in soil compared to air, which indicated deposition in soil. This could be because of the fallout of high-molecular-weight compounds. During the monsoons, PAH concentrations in the air were the lowest compared to the other seasons because of the dilution effect. Phenanthrene, fluoranthene, and pyrenes were dominant in the air, contributing up to 32.5%, 22.7%, and 19.2% of total PAHs, respectively. On the other hand, soils contained fluoranthene (12.3%), pyrene (10.7%), benzo[b]fluoranthene (10%), chrysene (9.82%), and indeno[123-c,d]pyrene (9.64%) compounds. The occurrence of indeno[1,2,3-cd]pyrene (9.14 ng/g) indicated that the soil is contaminated from fly ash and diesel emissions from the thermal power plant and vehicular emission. The diagnostic ratios, thematic maps, and principal component analysis revealed that the fly ash, diesel emissions from the thermal power plant, vehicles, and biomass burning were the probable sources of PAHs in the study area. The human health risk assessment studies reveal that the soil samples are more prone to carcinogenicity than air samples. As per our knowledge, this is the first report on the impact of PAHs on air and soil in this region.

Organic micropollutants in the surface riverine sediment along the lower stretch of the transboundary river Ganga: Occurrences, sources and ecological risk assessment.

The Hooghly River (HR) estuary is the first deltaic off-shoot of the perennial and transboundary river, Ganga, India. HR receives industrial and domestic waste along with storm-water run-off from Kolkata city and the adjoining districts. Organic micropollutants (OMPs) have been collectively termed for plasticizers, pharmaceuticals and personal care products, which are extensively consumed and disposed in the waste streams. Hence emerging OMPs were investigated to obtain the first baseline data from the Hooghly riverine sediment (HRS) along urban and suburban transects using gas chromatography mass spectrometry (GC-MS). The concentration range of OMPs in the HRS varied between 3 and 519 ng/g for carbamazepine, 5-407 ng/g for non-steroidal anti-inflammatory drugs (NSAIDs), 2-26 ng/g for musk ketone, 2-84 ng/g for triclosan, 2-199 ng/g for bisphenol A (BPA), 2-422 ng/g for plasticizers (phthalic acid esters (PAEs) and bis (2-ethylhexyl) adipate (DEHA)) and 87-593 ng/g for parabens. Carbamazepine concentration in sediment was an useful marker for untreated wastewater in urban waterways. High concentrations of BPA and PAEs in the suburban industrial corridor together with significant correlation between these two type of OMPs (r2 = 0.5; p < 0.01) likely reflect a common source, possibly associated with the plastic and electronic scrap recycling industries. Among all the categories of OMPs, plasticizers seems to exhibit maximum screening level ecological risk through out the study area.

Baseline investigation on plasticizers, bisphenol A, polycyclic aromatic hydrocarbons and heavy metals in the surface soil of the informal electronic waste recycling workshops and nearby open dumpsites in Indian metropolitan cities.

Electronic waste (e-waste) has emerged as a global environmental problem because of its massive production volume and un-structured management policy. Since the rate of e-waste accumulation is startling and the combinatorial effects of toxicants are complex, we have investigated six phthalic acid esters (PAEs), bis (2-ethylhexyl) adipate (DEHA)), bisphenol A (BPA), sixteen polycyclic aromatic hydrocarbons (PAHs) and eight heavy metals (HMs) in the surface soil of e-waste recycling workshops and nearby open dumpsites in four metropolitan cities of India viz., New Delhi (north), Kolkata (east), Mumbai (west) and Chennai (south). Average concentration of ∑16PAHs (1259 ng/g), ∑6PAEs (396 ng/g), BPA (140 ng/g) and ∑8HM (1288 mg/kg) in the informal e-waste recycling sites were higher than ∑16PAHs (1029 ng/g), ∑6PAEs (93 ng/g), BPA (121 ng/g) and ∑8HM (675 mg/kg) in dumpsites. Almost 50-90% of BPA, bis (2-ethylhexyl) phthalate (DEHP), ∑7carcPAHs and copper (Cu) were from e-waste sites predominantly from metal recovery sites (EWR). Extensive combustion of e-waste particularly in the EWR sites at New Moore market and Pudupet in Chennai and Wire Lane, Kurla of Mumbai can explain the segregation of diethyl phthalate (DEP), benzyl butyl phthalate (BBP) and carcinogenic PAHs in the first principal component (PC-1). Copper and lead along with highly abundant plasticizers like DEHP, dibutyl phthalate (DBP) and BPA were loaded in PC-2. Combined impact of burning the plastic cables in e-waste and acid leaching process especially at Mandoli in New Delhi might have driven this result. Loading of chrysene, DEHA and low molecular weight (LMW) PAHs mostly in dumpsite soil might have resulted from incomplete combustion of dumped e-waste. Copper was found to exhibit the highest pollution estimated by geo-accumulation index (Igeo). Maximum estimated carcinogenic risk for adults via dermal contact was due to copper, followed by chromium, lead and nickel.

Evaluating spatial distribution and seasonal variation of phthalates using passive air sampling in southern India.

Usage of phthalates as plasticizers has resulted in worldwide occurrence and is becoming a serious concern to human health and environment. However, studies on phthalates in Indian atmosphere are lacking. Therefore, we studied the spatio-temporal trends of six major phthalates in Tamil Nadu, southern India, using passive air samplers. Phthalates were ubiquitously detected in all the samples and the average total phthalates found in decreasing order is pre-monsoon (61 ng m-3) > summer (52 ng m-3) > monsoon (17 ng m-3). Largely used phthalates, dibutylphthalate (DBP) and diethylhexlphthalate (DEHP) were predominantly found in all the seasons with contribution of 11-31% and 59-68%, respectively. The highest total phthalates was observed in summer at an urban location (836 ng m-3). Furthermore, through principal component analysis, potential sources were identified as emissions from additives of plasticizers in the polymer industry and the productions of adhesives, building materials and vinyl flooring. Although inhalation exposure of infants was higher than other population segments (toddlers, children and adults), exposure levels were found to be safe for people belonging to all ages based on reference dose (RfD) and tolerable daily intake (TDI) values. This study first attempted to report seasonal trend based on atmospheric monitoring using passive air sampling technique and exposure risk together.

Polychlorinated biphenyls and organochlorine pesticides in River Brahmaputra from the outer Himalayan Range and River Hooghly emptying into the Bay of Bengal: Occurrence, sources and ecotoxicological risk assessment.

River Brahmaputra (RB) from the outer Himalayan Range and River Hooghly (RH), a distributary of River Ganga, are the two largest transboundary perennial rivers supplying freshwater to the northeastern and eastern states of India. Given the history of extensive usage of organochlorine pesticides and increasing industrialization along the banks of these rivers we investigated selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in the surface water of River Brahmaputra and River Hooghly. Geomean of ΣOCPs (53 ng L-1) and Σ19PCBs (108 ng L-1) was higher in RH compared with geomean of ΣOCPs (24 ng L-1) and Σ19PCBs (77 ng L-1) in RB. Among OCPs, γ-HCH showed maximum detection frequency in both the rivers reflecting ongoing lindane usage. DDT and endosulfan residues were observed at specific locations where past or ongoing sources exist. Elevated concentrations of heavier congeners (penta-hepta) were observed in those sites along RH where port and industrial activities were prevalent including informal electronic waste scrap processing units. Furthermore along River Hooghly PCB-126 was high in the suburban industrial belt of Howrah district. PCBs were found to be ubiquitously distributed in RB. Atmospheric transport of tri- and tetra-PCB congeners from the primary source regions might be a major contributor for PCBs in RB. Heavier congeners (penta-nona) in the urban centers of RB were likely due to industrial wastewater runoff from the oil refineries in the Brahmaputra valley. Σ19PCBs concentrations in this study exceeded the USEPA recommended limit for freshwater. Ecotoxicological risk assessment showed the possibility of adverse impact on the organisms in the lower trophic level due to DDT and lindane contamination. Impact of endosulfan on fishes might be of considerable concern for aquatic environment.

Phthalate esters in water and sediments of the Kaveri River, India: environmental levels and ecotoxicological evaluations.

Phthalate esters are well known for their environmental contamination and toxicological effects as "endocrine disruptors." In this study, environmental levels of phthalate esters and ecotoxicological risk assessments were performed in one of the major rivers in India, the Kaveri. Water and sediment samples were collected during 2010-2012 representing the major stretch of the river and extracted by solid-phase and ultrasonic methods, respectively, and analyzed for six major phthalates by using a gas chromatograph-mass spectrometer. The analytical recovery for phthalates in water and sediment ranged from 79 to 121%. Results indicated that diethyl phthalate (DEP) and dimethyl phthalate were found in every sample, whereas butylbenzyl phthalate and diethylhexyl phthalate (DEHP) were detected in 92% of the water samples. Likewise, in sediment samples, DEP was found most often (94%). The total phthalates in water samples ranged from 313 to 1,640 ng/l, whereas in sediments it was 2 to 1,438 ng/g dw (dry weight) with DEHP having the highest concentration. Human health risk assessment based on drinking water consumption showed no potential risk for phthalates and also DEHP levels were safe with respect to USEPA guideline (6,000 ng/l). Further, DEHP and di-n-octyl phthalate levels in water were expected to pose little threat to sensitive organisms in the riverine ecosystem as per ECOSAR chronic values. In case of sediment, the DEHP concentration was well above the USEPA sediment guideline value. To our knowledge, this is the first study to describe the levels and ecotoxicological risks of phthalates in Kaveri River, India.

GC-MS determination of bisphenol A and alkylphenol ethoxylates in river water from India and their ecotoxicological risk assessment.

Water samples from three rivers in southern India were analyzed for octylphenol (OP), nonylphenol (NP), and bisphenol A (BPA) residues by gas chromatography and mass spectrometry. The concentrations of OP, NP and BPA ranged from ND (not detected) to 16.3 ng/L, ND to 2200 ng/L, and 2.8 to 136 ng/L with detection frequencies of 96%, 66% and 100%, respectively. All three rivers showed a similar distribution pattern of NP>>BPA>OP, however, the Kaveri river had elevated levels. The phenolic compounds in rivers are expected to cause potential toxicity to aquatic organism including crustaceans, molluscs, insects and fish. In respect to aquatic risk assessment, NP showed a greater hazard quotient (HQ) than did OP and BPA, and the highest HQ (62) was observed for fish in the Kaveri river. The backwater and estuarine NP levels may pose a risk to larvae of oysters and barnacles. Based on tolerable daily intake and reference dose, BPA and NP levels are considered safe for humans. However, NP levels in some water samples were greater than the drinking water safety limit (0.5 µg/L). This is the first report on phenolic compounds and their associated aquatic risks in Indian rivers.

Non-steroidal anti-inflammatory drugs in Indian rivers.

Pharmaceutical concentration data for Indian surface waters are currently scarce. Sewage often enters Indian rivers without prior treatment, and so previously reported environmental concentrations from regions with routinely implemented sewage treatment cannot simply be used to predict concentrations in Indian surface water. Improved knowledge of pharmaceutical concentrations in Indian waters would enable determination of potential risks posed to aquatic wildlife and human health in this region. The concentrations of five common non-steroidal anti-inflammatory drugs (NSAIDs; diclofenac, ketoprofen, naproxen, ibuprofen, and acetylsalicylic acid) were determined in surface waters from 27 locations of the Kaveri, Vellar, and Tamiraparani Rivers in southern India. The samples were extracted by solid-phase extraction and analyzed by GC-MS. The measured concentrations of four of the five drugs in this reconnaissance were relatively similar to those reported elsewhere (ND-200 ng/l); however, acetylsalicylic acid, the most readily degradable of the investigated drugs, was found at all sites and at considerably higher concentrations (up to 660 ng/l) than reported in European surface waters. This is the first report on the occurrence of NSAIDs in Indian rivers. The finding of elevated concentrations of acetylsalicylic acid is most likely a result of direct discharges of untreated sewage. Therefore, readily degradable pharmaceuticals may present larger concern in regions without consistent sewage treatment. Based on measured environmental concentrations, the risks of direct toxicity to aquatic wildlife and of humans consuming the water are discussed.

Paraben resistance in bacteria from sewage treatment plant effluents in India.

Parabens, the antimicrobial preservatives used in cosmetics, food and pharmaceuticals, are often detected in the aquatic environment. Generally, sewage treatment plants (STPs) receive community sewage containing parabens, which are ultimately released into streams/rivers. In this study, bacteria in STP effluents were evaluated for their resistance to parabens. The susceptibility was in the order of Staphylococcus aureus > Bacillus sp. >Escherichia coli > Pseudomonas aeruginosa. Gram-negative bacteria showed less susceptibility than their control and Gram-positive bacteria. Further, the bacteria were more sensitive towards butyl and ethyl parabens. Interestingly, the strains showed resistance to ≥5 mg of parabens, which is equivalent to or higher than reported environmental concentrations. The increase in paraben chain length did not enhance the susceptibility in all cases and it was understood that the activity may differ for each bacterium in the environment. This is the first profile on paraben resistance in common pathogens of Indian STPs. Paraben resistance may be developed due to continuous exposure even at sub-inhibitory and/or chronic levels in the environment and this resistance may be transferred to other pathogenic bacteria in receiving waters. Thus the study demonstrates the effectiveness of the disc diffusion method in environmental bacterial resistance assessment and addresses the risk involved in the use of parabens.