Aromatic amine antioxidants (AAs) and p-phenylenediamines-quinones (PPD-Qs) in e-waste recycling industry park: Occupational exposure and liver X receptors (LXRs) disruption potential.

Recently, evidence of aromatic amine antioxidants (AAs) existence in the dust of the electronic waste (e-waste) dismantling area has been exposed. However, there are limited studies investigating occupational exposure and toxicity associated with AAs and their transformation products (p-phenylenediamines-quinones, i.e., PPD-Qs). In this study, 115 dust and 42 hand wipe samples collected from an e-waste recycling industrial park in central China were analyzed for 19 AAs and 6 PPD-Qs. Notably, the median concentration of ∑6PPD-Qs (1,110 ng/g and 1,970 ng/m2) was significantly higher (p < 0.05, Mann-Whitney U test) than that of ∑6PPDs (147 ng/g and 34.0 ng/m2) in dust and hand wipes. Among the detected analytes, 4-phenylaminodiphenylamine quinone (DPPD-Q) (median: 781 ng/g) and 1,4-Bis(2-naphthylamino) benzene quinone (DNPD-Q) (median: 156 ng/g), were particularly prominent, which were first detected in the e-waste dismantling area. Occupational exposure assessments and nuclear receptor interference ability, conducted through estimated daily intake (EDI) and molecular docking analysis, respectively, indicated significant occupational exposure to PPD-Qs and suggested prioritized Liver X receptors (LXRs) disruption potential of PPDs and PPD-Qs. The study provides the first evidence of considerable levels of AAs and PPD-Qs in the e-waste-related hand wipe samples and underscores the importance of assessing occupational exposure and associated toxicity effects.

Nontarget Identification of Novel Per- and Polyfluoroalkyl Substances (PFAS) in Soils from an Oil Refinery in Southwestern China: A Combined Approach with TOP Assay.

Oil refinery activity can be an emission source of perfluoroalkyl and polyfluoroalkyl substances (PFAS) to the environment, while the contamination profiles in soils remain unknown. This study investigated 44 target PFAS in soil samples collected from an oil refinery in Southeastern China, identified novel PFAS, and characterized their behaviors by assessing their changes before and after employing advanced oxidation using a combination of nontarget analysis and a total oxidizable precursor (TOP) assay. Thirty-four target PFAS were detected in soil samples. Trifluoroacetic acid (TFA) and hexafluoropropylene oxide dimer acid (HFPO-DA) were the dominant PFAS. Twenty-three novel PFAS of 14 classes were identified, including 8 precursors, 11 products, and 4 stable PFAS characterized by the TOP assay. Particularly, three per-/polyfluorinated alcohols were identified for the first time, and hexafluoroisopropanol (HFIP) quantified up to 657 ng/g dw is a novel precursor for TFA. Bistriflimide (NTf2) potentially associated with an oil refinery was also reported for the first time in the soil samples. This study highlighted the advantage of embedding the TOP assay in nontarget analysis to reveal not only the presence of unknown PFAS but also their roles in environmental processes. Overall, this approach provides an efficient way to uncover contamination profiles of PFAS especially in source-impacted areas.

Distribution, bioaccumulation, and health risk assessment of organochlorines across the riverine ecosystem of Punjab Province, Pakistan.

This study was designed to assess the distribution of organochlorines (OCs) in fish species, their spatio-temporal variations, bioaccumulation potential, and associated human health risks via dietary intake. The levels of twenty-three organochlorine pesticides (OCPs) and thirty-five polychlorinated biphenyls (PCBs) were analyzed in six fish species collected from the riverine ecosystem of Punjab Province, Pakistan. The results indicated that the mean levels of Σ23OCPs were 74.1 ng/g ww and 184 ng/g ww, and for Σ35PCBs the levels were 38.8 ng/g ww and 74.8 ng/g ww in herbivorous and carnivorous fish species, respectively. The most abundant contaminants in all fish species were DDTs (65%) and HCHs (14%) among OCPs and heavier PCB congeners (62%) among PCBs. As for dioxin-like PCBs, the WHO toxic equivalency values (ng TEQ/g ww) were in the range of 0.21 (Cyprinus Carpio) to 2.38 (Rita Rita), exceeding the maximum allowable limit of 0.004 ng TEQ/g, ww by the European Commission. Spatio-temporal analysis indicated relatively higher OC levels in winter season with elevated concentrations in fish samples from industrial zone. The bioconcentration factor (L/kg) values ranged from 723 to 2773 for PCBs and 315 to 923 for OCPs in all fish species, with higher levels were reported in carnivorous species. The human health risk assessment at both 50th and 95th percentiles revealed the absence of any significant non-carcinogenic risk as calculated HR was less than 1. However, the critical carcinogenic risk was found to be associated for most of the contaminants, signifying the dietary exposure to OCPs and PCBs might pose the public health concern.

Association of human cohorts exposed to blood and urinary biomarkers of PAHs with adult asthma in a South Asian metropolitan city.

Semi-volatile organic compounds (SVOCs) are a major global problem that causes the greatest impact on urban settings and have been linked to bronchial asthma in both children and adults in Pakistan. The association between exposure of polycyclic aromatic hydrocarbons (PAHs) and asthma in the adult population is less clear. The current study aimed to assess the clinico-chemical parameters and blood levels of naphthalene phenanthrene, pyrene, and 1,2-benzanthracene and urinary levels of 1-OH pyrene and 1-OH phenanthrene as well as asthma-related biomarkers immunoglobulin E (IgE), resistin, and superoxide dismutase (SOD) of oxidative stress and other hematologic parameters in adults and their relationship with bronchial asthma. The GC/MS analysis showed higher mean concentrations of blood PAHs in asthma respondents (4.48 ± 1.34, 3.46 ± 1.04, 0.10 ± 0.03, and 0.29 ± 0.09) (ng/mL) as compared to controls (3.07 ± 0.92, 1.71 ± 0.51, 0.06 ± 0.02, and 0.11 ± 0.03) (ng/mL), with p = .006, p = .001, p = .050, and p = .001. Similarly, urinary levels of 1-OHpyr and 1-OHphe were significantly increased in adults with bronchial asthma (0.54 ± 0.16; 0.13 ± 0.04) (µmol/mol-Cr) than in controls (0.30 ± 0.09; 0.05 ± 0.02) (µmol/mol-Cr), with p = .002 and p = .0001, respectively, with a significant positive correlation to asthma severity. The asthma-related biomarkers IgE, resistin, and SOD were significantly higher (p 0.0001, 0.0001, and 0.0001) in people with asthma than in control persons. The findings showed that higher blood and urine PAHs levels were linked to higher asthma risk in adults and significant interaction with participants who smoked, had allergies, had a family history of asthma, and were exposed to dust. The current study's findings will be useful to local regulatory agencies in Lahore in terms of managing exposure and advocating efforts to minimize PAH pollution and manage health.

Source identification and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in air and dust samples of Lahore City.

During two consecutive summer and winter seasons in Lahore, the health risk of air and dust-borne polycyclic aromatic hydrocarbons (PAHs) was evaluated. Gas chromatography/mass spectrometry (GS/MS) was used to determine air and dust samples from various functional areas across the city. The mean ∑16PAHs were higher in air 1035.8 ± 310.7 (pg m-3) and dust 963.4 ± 289.0 (ng g-1 d.w.) during winter seasons as compared to summer seasons in air 1010.9 ± 303.3 (pg m-3) and dust matrices 945.2 ± 283.6 (ng g-1 d.w.), respectively. PAHs ring profile recognized 3 and 4 rings PAHs as most dominant in air and dust samples. Estimated results of incremental lifetime cancer risk (ILCR) highlighted high carcinogenic risk among the residents of Lahore via ingestion and dermal contact on exposure to atmospheric PAHs. The total ILCR values in air among children (summer: 9.61E - 02, winter: 2.09E - 02) and adults (summer: 1.45E - 01, winter: 3.14E - 02) and in dust, children (summer: 9.16E - 03, winter: 8.80E - 03) and adults (summer: 1.38E - 02, winter: 1.33E - 02) during the study period. The isomeric ratios in the study area revealed mixed PAH sources, including vehicular emission, petroleum, diesel and biomass combustion. As a result, it is advised that atmospheric PAHs should be monitored throughout the year and the ecologically friendly fuels be used to prevent PAHs pollution and health concerns in the city. The findings of this study are beneficial to the local regulating bodies in terms of controlling the exposure and promoting steps to reduce PAHs pollution and manage health in Lahore.

Assessment of organochlorine pesticides and health risk in tobacco farming associated with River Barandu of Pakistan.

Diffuse pesticide pollution through tobacco fields is a serious threat to both natural integrities and living beings because tobacco is known as a pesticide-intensive crop. Upsurge in the knowledge of detrimental impacts caused by organochlorine pesticides (OCPs) has made them a burning issue particularly in developing countries. Pakistan is a country famous for its agro-based economy and simultaneously is the second most significant pesticide consumer in South Asian countries. The studied area is tobacco hub of the country. Thus, the present work is aimed to investigate the contamination profile that highlights the ecological and health risk posed by OCPs in River Barandu, located in the proximity of tobacco farming region. ΣOCP levels in sediments ranged between 32.918 and 98.810 ng/g and in water between 0.340 and 0.935 µg/L. Hexachlorocyclohexanes (HCHs) and heptachlor were the most prevailing pesticides in both matrices of the river. Isomeric composition of DDTs and HCHs highlighted that the ß-HCH and p,p'-DDT were dominant isomers in water, while α-HCH and p,p'-DDT in sediment compartment. Enantiomeric compositions of HCH and DDT indicate both recent and historic uses of these compounds in the area. Indirect contamination through nearby tobacco clusters has been depicted through spatial analysis. Ecological risk assessment based upon the risk quotient (RQ) method revealed that α-endosulfan, dieldrin, heptachlor, and ∑HCHs represent a very high level of ecological risks. The OCPs' lifetime carcinogenic and non-carcinogenic health risks associated with dermal exposure to river's water were considered nominal for surrounding populations. However, detailed ecological and health risk studies are recommended considering the bio-accumulating nature of these contaminants in the food chain.

Polychlorinated biphenyls in indoor dust from urban dwellings of Lahore, Pakistan: Congener profile, toxicity equivalency, and human health implications.

This study is the pioneer assessment of the PCBs in indoor dust particles (from air conditioners) of an urbanized megacity from South Asian. The ∑35 PCB concentration ranged from 0.27 to 152.9 ng/g (mean: 24.84 ± 22.10 ng/g). The tri- and tetra-PCBs were dominant homologues, contributing 57.36% of the total PCB concentrations. The mean levels of Σ8 -dioxin-like (DL), Σ6 -indicator PCBs and WHO2005 -TEQ for DL-PCBs were 2.22 ± 2.55 ng/g, 9.49 ± 8.04 ng/g and 4.77 ± 4.89 pg/g, respectively. The multiple linear regression indicated a significant correlation of dusting frequency (p = 1.06 × 10-04) and age of the house (p = 1.02 × 10-06) with PCB concentrations in indoor environment. The spatial variation of PCB profile revealed relatively higher concentrations from sites near to illegal waste burning spots, electrical locomotive workshops, and grid stations. Human health risk assessment of PCBs for adults and toddlers through all three exposure routes (ie, inhalation, ingestion, and dermal contact) demonstrated that toddlers were vulnerable to high cancer risk (4.32 × 10-04 ), while adults were susceptible from low to moderate levels of risk (3.16 × 10-05 ). Therefore, comprehensive investigations for PCBs in the indoor settings, focusing particularly on the sensitive populations with relationship to the electronic devices, transformers, and illegal waste burning sites, are recommended.

Organochlorine pesticides (OCPs) in air-conditioner filter dust of indoor urban setting: Implication for health risk in a developing country.

This preliminary investigation highlights the occurrence of organochlorine pesticides (OCPs) in the indoor environment of a megacity, Lahore, Pakistan using the dust ensnared by air-conditioner filters. The Σ16 OCPs concentration ranged from 7.53 to 1272.87 ng/g with the highest percent contribution by ΣDDT (dichlorodiphenyltrichloroethane; 87.21%) and aldrin (6.58%). The spatial variation of OCPs profile revealed relatively higher concentration from homes near to agricultural and abandoned DDT manufacturing sites. Calculated isomer ratios revealed historic sources of hexachlorocyclohexanes (HCHs) and the fresh input of technical DDT and chlordane by the dwellers. The air conditioner dust was helpful to better understand the health risk in the indoor environment. So far a high lifetime cancer risk (10-3 ) was predicted for toddlers via accidental ingestion, inhalation, and dermal exposure. Similarly, the non-carcinogenic risk-based hazard quotient was found to be high for toddlers (6.94) and within the permissible limit (<1) for adults.

Organochlorine pesticides in the surrounding soils of POPs destruction facility: source fingerprinting, human health, and ecological risks assessment.

The elimination of persistent organic pollutants (POPs) obsolete pesticides stockpiles, particularly the organochlorine pesticides (OCPs), is one of the critical environmental issues faced by many developing countries. This pioneering study aimed to investigate the occurrence, source fingerprinting, human health, and ecological risks of OCPs in the surroundings of the lone POPs pesticide destruction facility in Pakistan. The ΣOCPs residual levels in soil ranged from 35.98 to 566.77 ng/g dry weight (dw), with a mean concentration of 174.42 + 111.62 ng/g (dw). The OCPs contamination levels in the soil followed the pattern as ΣHCHs > Σendrins > Σendosulfans > dieldrin > Σheptachlors > ΣDDTs > Σchlordanes > methoxychlor. The ΣHCHs residual concentrations were comparatively higher than the previous national and global soil studies. The recent accumulation of HCHs, DDTs, and heptachlor was observed in the study area as identified by ß-HCH/∑HCHs, (DDE + DDD)/ΣDDTs, heptachlor/Σheptachlor, and heptachlor exo-epoxide/heptachlor ratios. The OCPs' lifetime carcinogenic risk through ingestion, dermal, and inhalation exposure routes ranged from 1.65E-08 to 2.91E-07, whereas the noncarcinogenic hazard quotient (HQ) ranged from 9.12E-05 to 1.61E-03. The risk vulnerability among age groups was in the order: adult > toddler > child > teen > infant. The calculated risk levels were within an acceptable limit of one in a million (1 × 10-6) for carcinogenic risk and HQ < 1 for noncarcinogenic risk. The current OCPs residual levels, especially dieldrin and endrin, exhibited low to medium ecological risks when compared to various worldwide limits. The upsurge of the OCPs' environmental contamination levels over the years and consideration of the food chain transfer might amplify the human health and ecological risks intensities.

Assessment of organochlorine pesticides in the Himalayan riverine ecosystems from Pakistan using passive sampling techniques.

Organochlorine pesticides (OCPs) pose a considerable threat to human and environmental health. Despite most OCPs have been banned, they are still reported to be used in developing countries, including Pakistan. We aimed to identify the distribution, origin, mobility, and potential risks from OCPs in three major environmental compartments, i.e., air, water, and soil, across Azad Jammu and Kashmir valley, Pakistan. The sums of OCPs ranged between 66 and 530 pg/g in soil, 5 and 13 pg/L in surface water, and 14 and 191 pg/m3 in air, respectively. The highest sum of OCPs was observed in the downstream zone of a river that was predominantly influenced by peri-urban and urban areas. The OCP isomers ratios (α-HCH/γ-HCH and o,p'-DDT/p,p'-DDT) indicate use of lindane and technical DDTs mixture as a source of HCH and DDT in the riverine environment. Similarly, the ratios of DDE and DDD/the sum of DDTs, α-endosulfan/ß-endosulfan, and cis-chlordane/trans-chlordane indicate recent use of DDTs, endosulfan, and chlordane in the region. The air-water exchange fugacity ratios indicate net volatilization (fw/fa > 1) of α-endosulfan and trans-chlordane, and net deposition (fw/fa < 1) of ß-endosulfan, α-HCH, γ-HCH p,p'-DDD, p,p'-DDE, and p,p'-DDT. Based on the risk quotient (RQ) method, we consider the acute ecological risks for fish associated with the levels of OCPs as negligible. However, more studies are recommended to evaluate the chronic ecological risks to other riverine-associated aquatic and terrestrial species as well as human health risks to the POPs exposure through food chain transfer in forthcoming years.

Organochlorine pesticides across the tributaries of River Ravi, Pakistan: Human health risk assessment through dermal exposure, ecological risks, source fingerprints and spatio-temporal distribution.

This study monitored the human health risks through dermal exposure, hazardous risks to ecological integrity, contamination levels, spatio-temporal distribution, and congener specific analysis of organochlorine pesticides (OCPs) across River Ravi and its three northern tributaries (Nullah Bein, Nullah Basanter and Nullah Deg). The residual levels of OCPs isomers were screened for water (n=54) and surface sediment (n=54) samples from twenty seven sampling sites in two alternate seasons (pre-monsoon and post-monsoon). The ∑OCPs concentrations ranged from 13.61 to 1992.18ng/g dry weight and 12.89 to 128.16ng/L with predominance of ß-endosulfan and p,p'-DDT in sediment and water matrixes, respectively. Distribution pattern revealed significantly higher concentrations in upstream and midstream, suggesting considerable transboundary OCPs pollution. Calculated ratios of α-HCH/γ-HCH, o,p'-DDT/p,p'-DDT, (DDE+DDD)/∑DDTs and cis/trans-chlordane for water and sediments identified the fresh addition of lindane, technical DDTs and chlordane in the study area. Risk quotient (RQ) based ecological risk was found to be >1 at all studied streams during both seasons and elucidates higher risks for endosulfan (α-endosulfan) and endrin. Human health risk assessment indicated absence of hazardous (non-carcinogenic) risk through bathing in studied streams; as the hazard index values ranged from 1.09E-05 to 2.48E-02 (acceptable limit; <1). However, the calculated carcinogenic risk possessed by OCPs through dermal exposure ranged from 1.39E-10 to 1.98E-05 that highlighted the considerable carcinogenic risk associated to aldrin, dieldrin, p,p'-DDT and ß-endosulfan at certain studied sites. Therefore, the high levels of ecological risk and carcinogenic human health risk had emphasized an immediate elimination of ongoing OCPs addition in the studied area.

Potential of miscanthus biochar to improve sandy soil health, in situ nickel immobilization in soil and nutritional quality of spinach.

The complex interaction of biochar (BC) with soil health reflecting properties, the feedstock used to prepare BC and application rate of BC in sandy soil is still a question for the researchers. An incubation study was conducted where nine different sorts of BC, each prepared from the different feedstock, were applied at 2% rate to evaluate their relative suitability to improve sandy soil health. Results revealed that BC prepared from miscanthus (MIB) significantly increased soil medium and fine pores, available water content (AWC), electrical conductivity (EC), and cation exchange capacity (CEC) while decreased soil wide pores, pH, bulk density (BD) and particle density (PD) compared to the rest sorts of BC. Later, spinach was grown in pots containing same soil but spiked with 50 ppm nickel (Ni) and amended with 1, 2, 3, 4 and 5% rates of MIB. The results showed a significant increment in spinach biomass, reduction in the concentrations of Ni in spinach tissues and DTPA-extractable Ni with the increasing rate of MIB till 3% and later, no significant changes with 4 and 5% rates thereafter. However, significant improvement in the activities of antioxidant enzymes, chemical and biochemical attributes of spinach were observed at 5% MIB when compared to lower rates. Similarly, post-harvest soil physicochemical and enzymatic parameters were also significantly (P < 0.05) improved with increasing rates of MIB. This study implies that application of MIB at 5% rate can improve the nutritional quality of spinach, sandy soil health and can reduce Ni concentrations in spinach tissues.

Phytoremediation of organochlorine and pyrethroid pesticides by aquatic macrophytes and algae in freshwater systems.

Extensive use of Pesticides in agriculture and its surface runoff in river water is a major environmental concern. The present study evaluated the phytoremediation potential of Eichornia crassipes, Pistia strateotes and algae (Chaetomorpha sutoria, Sirogonium sticticum and Zygnema sp.) for organochlorine and pyrethroid pesticides. Water and plant samples were extracted by liquid phase and solid phase extraction respectively and analyzed by high-performance liquid chromatography. Eleven treatments (T1-T11) with and without plants were used for phytoremediation of organochlorine and pyrethroid pesticides. During the experiment, P. strateotes, E. crassipes and algae (C. sutoria, S. sticticum and Zygnema sp.) showed the highest removal efficiency with 62 (71% root, 29% shoot), 60 (67% root, 33% shoot), and 58% respectively for organochlorine and 76 (76% root, 24% shoot), 68 (69% root, 31% shoot), and 70% respectively for pyrethroids for the respective aquatic plants. Dissipation rate constant of treatments with plants (T2, T3, T5, T6, T8, and T9) was significantly higher (p < 0.05) as compared to that of treatments without plants (T10 and T11, control) for both organochlorine and pyrethroid. The bioconcentration factor of pyrethroid treatments (T3, T6, and T9) was significantly higher (p < 0.05) as compared to that of organochlorine treatments (T2, T5 and T8). The removal efficiency of E. crassipes, P. strateotes and algae (C. sutoria, S. sticticum and Zygnema sp.) for pyrethroids was significantly higher (p < 0.01) as compared to that of organochlorine.