Correlation analysis between the in vivo bioavailability and in vitro bioaccessibility of nitro PAHs in soil: Application of simplified FOREhST in vitro methods based on the Chinese pharmacopoeia.

In this study, the relative bioavailability (RBA) of nitrated polycyclic aromatic hydrocarbons (NPAHs) in soil samples (n = 30) was assessed using an in vivo mouse model. Based on the correlation between the bioaccessibility data obtained from the Tenax improved traditional Fed ORganic Estimation human Simulation Test (FOREhST) in vitro method (TITF) and the bioavailability data obtained from in vivo experiments, the TITF method was further optimized and simplified by referring to the "Pharmacopoeia of the People's Republic of China: Volume IV, 2020" to adjust the formulation and parameters of the gastrointestinal fluid (GIF) in order to establish a simpler and lower cost in vitro method for the determination of the bioaccessibilities of NPAHs. The dose-accumulation relationship of the in vivo experiment showed that the linear dose-response was better in adipose tissue (R2 = 0.77-0.93), and the accumulation of NPAHs in adipose tissue was higher than that in kidney or liver tissue. Depending on the mouse adipose model, the NPAHs-RBA ranged from 1.88 % to 73.92 %, and a strongly significant negative relationship (R2 = 0.94, p < 0.05) was found between the NPAHs-RBA and Log Kow. The simplified experiment of the TITF showed that the composition of the GIF medium had a significant effect on the bioaccessibilities of NPAHs. The NPAH bioaccessibilities measured by the Tenax improved simplified FOREhST method (TISF) (9.0-36.5 %) were higher than that of the traditional FOREhST method (6.8-22.8 %) but significantly lower than that of the TITF method (16.8-55.2 %). With an increase in the bile concentration in the GIF (from 6 to 10 g/L), the bioaccessibilities of NPAHs increased from 9.0 to 36.5 % to 12.9-42.4 %. The accuracies of the four in vitro methods for predicting the bioavailabilities of NPAHs was in the following order: Tenax improved simplified FOREhST method with increased bile concentration (TITF-IB) (R2 = 0.54-0.87) ≈ TITF (R2 = 0.55-0.85) > TISF (R2 = 0.41-0.77) > FOREhST (R2 = 0.02-0.68). These results indicated that the simple in vitro method could also effectively predict the bioavailabilities of NPAHs.

Bioaccessibility and bioavailability of NPAHs in soils using in vitro-in vivo assays: Comparison of laboratory and outdoor environmental aging effect.

Aging process is one of the most important factors that markedly reduces bioaccessibility and bioavailability (bioac-bioav) of organic contaminants. However, only few data on comparison of the effects of laboratory artificial aging (LAA) and outdoor environmental aging (OEA) processes on nitrated polycyclic aromatic hydrocarbons (NPAHs) bioac-bioav are available. In the current study, oral bioac-bioav of NPAHs in LAA and OEA soils (aging time intervals: 0, 45, 90, 120 and 150 d) were measured by in vitro traditional Fed ORganic Estimation human Simulation Test (FOREhST) and Tenax improved FOREhST (TI-FOREhST) methods, and in vivo mouse model. Tenax significantly increased the bioaccessibility of NPAHs in freshly spiked and aging soils from 0.3-40.9 % to 15.6-95.3 %, and 0.3-40.9 % to 1.0-84.5 %, respectively. Aging significantly reduced the NPAHs bioaccessibility (from 36.5 % to 10.7 %, and 12.1 % to 5.1 % as measured by FOREhST and TI-FOREhST, respectively) and bioavailability (from 27.7 % to 9.9 %, as measured by mouse model). The changes in bioac-bioav were mainly observed within the first 120 d of aging. The statistical analyses of NPAHs bioac-bioav showed no significant difference (p > 0.05) among the aging time intervals in LAA and OEA soils, which demonstrated that the LAA can relatively represent the OEA. Determination of TOC content in LAA and OEA soil can intuitively reflect whether the difference of NPAHs bioac-bioav between two aging treatment groups is significant. The mean bioaccessibility of NPAHs in soil measured by TI-FOREhST (mean 20.6 %) is closer to the bioavailability measured by mouse model (mean 19.4 %), indicating that Tenax improved in vitro method is more reliable than traditional methods, to predict the bioavailability of NPAHs.

Evaluating the adsorption performance of Tenax TA® in different containers: An isolation tool to study the bioaccessibility of nitro-PAHs in spiked soil.

The improved in vitro gastrointestinal simulation methods, with the addition of the adsorption sink, are considered as a promising tool for predicting the bioaccessibility of contaminants. However, the problem associated with the recovery of the adsorption sink from the complex matrix needs more understand. Although previous studies tried to solve this shortcoming by using the containers (a vessel to hold the adsorption sink), there is no systematic comparison study on the impact of containers on bioaccessibility till now, especially for nitro-polycyclic aromatic hydrocarbons (nitro-PAHs). In order to understand the problem, commonly used containers in previous studies (dialysis bags and stainless-steel screen) were selected and deployed in the Fed Organic Estimation Human Simulation Test (FOREhST) method to compare the effects of these containers on the bioaccessibility of nitro-PAHs desorbed from the five different types of soils into the gastrointestinal fluid (GIF). Results showed that in order to maintain a constant sorptive gradient for the high molecular weight (MW) nitro-PAHs, 0.25 g of Tenax TA® were required in FOREhST. Compared with Tenax TA® encapsulated in dialysis bag (Tenax-EDBG), the use of Tenax TA® encapsulated in dissolution basket (Tenax-EDBT) significantly increased the bioaccessibility of nitro-PAHs in the soil from 5.6-31.4% to 17.2-70.6%, due to the better diffusion performance. The bioaccessibility of nitro-PAHs by FOREhST extraction with Tenax-EDBT showed a significant negative correlation with soil total organic carbon (TOC), whereas a weak correlation with pH. This study provides the researchers with a more standardized in vitro method to quantify the bioaccessibility of PAHs and their derivatives in soil.

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.

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.

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.

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.

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.

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.