Legacy and emerging flame retardants (FRs) in the urban atmosphere of Pakistan: Diurnal variations, gas-particle partitioning and human health exposure.

Atmospheric concentration of legacy (LFRs) and emerging flame retardants (EFRs) including 8 polybrominated diphenyl ethers (PBDEs), 6 novel brominated flame retardants (NBFRs), 2 dechlorane plus isomers (DP), and 8 chlorinated organophosphate flame retardants (OPFRs) were consecutively measured in eight major cities across Pakistan. A total of 96 samples (48 PM2.5 & 48 PUFs) were analyzed and the concentrations of ∑8PBDEs (gaseous+particulate) ranged between 40.8 and 288 pg/m3 with an average value of 172 pg/m3. ∑6NBFRs ranged between 12.0 and 35.0 pg/m3 with an average value of 22.5 pg/m3 while ∑8OPFRs ranged between 12,900-40,800 pg/m3 with an average of 24,700 pg/m3. Among the studied sites, Faisalabad city exhibited the higher concentrations of FRs among all cities which might be a consequence of textile mills and garment manufacturing industries. While analyzing the diurnal patterns, OPFRs depicted higher concentrations during night-time. The estimated risks of all groups of FRs from inhalation of ambient air were negligible for all the cities, according to USEPA guidelines. Nonetheless, our study is the first to report gaseous and particulate concentrations of FRs in air on a diurnal basis across major cities in Pakistan, offering insights into the atmospheric fate of these substances in urban areas in a sub-tropical region.

Oxidative stress risk assessment through heavy metal and arsenic exposure in terrestrial and aquatic bird species of Pakistan.

In this study, we investigated metal- and metalloid-induced oxidative stress response in two aquatic (cattle egret (Bubulcus ibis) (n = 10), pond heron (Ardeola grayii) (n = 10)), as well as two terrestrial (spotted owlet (Athene brama) (n = 6) and bank myna (Acridotheres ginginianus) (n = 16)) bird species collected from the outskirts of Lahore city, Pakistan. For this purpose, glutathione (tGSH) and lipid peroxidation (thiobarbituric acid-reactive substances (TBARS)) levels and activities of antioxidant enzymes (superoxide dismutase (SOD); catalase (CAT)) were analyzed as biomarkers of oxidative stress against metal (Pb, Cd, Cu, Zn) and metalloid (As) concentrations in kidney liver and blood of birds. Our results depicted significant correlation for Pb, Cd, and As with oxidative stress biomarkers in birds. The levels of heavy metals and As and their corresponding effects on oxidative stress biomarkers were comparably higher in aquatic species (p ≤ 0.01) except for Pb and Zn. In comparison of species, SOD and tGSH activities were higher in bank myna and cattle egret, while CAT activity and TBARS concentrations were higher in pond heron and cattle egret, respectively. We deduced that tissues with higher accumulation of metal(loid)s such as liver and kidney were under a great risk to oxidative damage. The overall order of metal accumulation and subsequent oxidative damage among families followed the pattern as Strigidae ≥Ardieda ≥ Sturnidae with their respective trophic levels. Globally, metal- and As-induced oxidative stress is least emphasized in multiple tissues of birds that is needed to be addressed with focus on case-control studies using dose-response approach. Graphical abstract .

E-Waste Driven Pollution in Pakistan: The First Evidence of Environmental and Human Exposure to Flame Retardants (FRs) in Karachi City.

Informal e-waste recycling activities have been shown to be a major emitter of organic flame retardants (FRs), contributing to both environmental and human exposure to laborers at e-waste recycling sites in some West African countries, as well as in China and India. The main objective of this study was to determine the levels of selected organic FRs in both air and soil samples collected from areas with intensive informal e-waste recycling activities in Karachi, Pakistan. Dechlorane Plus (DP) and "novel" brominated flame retardants (NBFRs) were often detected in high concentrations in soils, while phosphorus-based FRs (OPFRs) dominated atmospheric samples. Among individual substances and substance groups, decabromodiphenyl ether (BDE-209) (726 ng/g), decabromodiphenyl ethane (DBDPE) (551 ng/g), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE) (362 ng/g), and triphenyl-phosphate (∑TPP) (296 ng/g) were found to be prevalent in soils, while OPFR congeners (5903-24986 ng/m3) were prevalent in air. The two major e-waste recycling areas (Shershah and Lyari) were highly contaminated with FRs, suggesting informal e-waste recycling activities as a major emission source of FRs in the environment in Karachi City. However, the hazards associated with exposure to PM2.5 appear to exceed those attributed to exposure to selected FRs via inhalation and soil ingestion.

The first exposure assessment of legacy and unrestricted brominated flame retardants in predatory birds of Pakistan.

The exposure to legacy polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and unrestricted 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), bis (2-ethylhexyl)-2,3,4,5-tetrabromophthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5-tetrabromo-benzoate (EH-TBB) was examined in tail feathers of 76 birds belonging to ten predatory species inhabiting Pakistan. In addition, different feather types of six individuals of Black kite (Milvus migrans) were compared for their brominated flame retardant (BFR) levels. Black kite was found to be the most contaminated species with a median (minimum-maximum) tail feather concentration of 2.4 (0.70-7.5) ng g-1 dw for ∑PBDEs, 1.5 (0.5-8.1) ng g-1 dw for ∑HBCDDs and 0.10 ( 0.05 for both). Similarly, no significant concentration differences were observed among different feather types (all P > 0.05) suggesting their similar exposure. While variables such as species, trophic guild and δ15N values were evaluated as major predictors for BFR accumulation in the studied species, we predict that combined effects of just mentioned factors may govern the intra- and interspecific differences in BFR contamination profiles. We urge for further investigation of BFR exposure and potential toxicological effects in predatory birds from Asia with a more extensive sample size per species and location.

Use of feathers to assess polychlorinated biphenyl and organochlorine pesticide exposure in top predatory bird species of Pakistan.

Little is known about the levels of organochlorines (OCs) in predatory bird species from Asia or the factors governing their concentrations. This study is the first report on concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in predatory birds of Pakistan. The concentrations of PCBs and OCPs were investigated using tail feathers of ten different species of predatory birds. In addition, concentration differences among body, tail, primary and secondary feathers were investigated for six individuals of black kite (Milvus migrans). Ranges of concentrations were highest for dichlorodiphenyldichloroethylene (p,p'-DDE: 0.11-2163ngg(-1) dry wt.) followed by dichlorodiphenyltrichloroethane (p,p'-DDT: 0.36-345ngg(-1) dry wt.), hexachlorobenzene (HCB: 0.02-34ngg(-1) dry wt.), ∑PCBs (0.03-16ngg(-1) dry wt.) and trans-nonachlor (TN; 0.01-0.13ngg(-1) dry wt.). CB 118, 153, 138, and 180 along with p,p'-DDE were found as the most prevalent compounds. ∑PCBs and ∑DDTs were significantly different among species (both p<0.01) and omnivorous, scavengers, carnivorous and piscivorous trophic guilds (all p<0.03). Only ∑PCBs were significantly differentamong different families of birds (p<0.01). Values of stable isotopes (δ(13)C and δ(15)N) differed significantly (all p<0.01) among species, families, trophic guilds as well as terrestrial and aquatic habitat but not between nocturnal and diurnal predators (p=0.22 for δ(13)C; p=0.50 for δ(15)N). Concentrations of ∑PCBs, ∑DDTs and trans-nonachlor, but not HCB (p=0.86), were significantly different among different feather types (all p<0.01). Trophic and taxonomic affiliation as well as dietary carbon sources (δ(13)C) for species were identified as the variables best explaining the observed variation in exposure to the studied compounds. The significance of contributing factors responsible for OC contamination differences in predatory birds should be further elucidated in future studies.

Organochlorine pesticides (OCPs) in the Indus River catchment area, Pakistan: Status, soil-air exchange and black carbon mediated distribution.

Organochlorine pesticides (OCPs) were investigated in passive air and soil samples from the catchment area of the Indus River, Pakistan. ∑15OCPs ranged between 0.68 and 13.47 ng g(-1) in soil and 375.1-1975 pg m-(3) in air. HCHs and DDTs were more prevalent in soil and air compartments. Composition profile indicated that ß-HCH and p,p'-DDE were the dominant of all metabolites among HCHs and DDTs respectively. Moreover, fBC and fTOC were assessed and evaluated their potential role in the distribution status of OCPs. The fTOC and fBC ranged between 0.77 and 2.43 and 0.04-0.30% respectively in soil. Regression analysis showed the strong influence of fBC than fTOC on the distribution of OCPs in the Indus River catchment area soil. Equilibrium status was observed for ß-HCH, δ-HCH, p,p'-DDD, o,p'-DDT, TC, HCB and Heptachlor with ff ranged between 0.3 and 0.59 while assessing the soil-air exchange of OCPs.

Concentrations and patterns of organochlorines (OCs) in various fish species from the Indus River, Pakistan: A human health risk assessment.

The present study was conducted to reveal the concentrations and patterns of organochlorines [i.e., organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs)] in freshwater fish species collected from four ecologically important sites of the Indus River i.e., Taunsa (TAU), Rahim Yar Khan (RYK), Guddu (GUD) and Sukkur (SUK). In the fish muscle tissues, concentrations of 15 OCPs (∑15OCPs) and 29 PCBs (∑29PCBs) varied between 1.93-61.9 and 0.81-44.2 ng/g wet weight (ww), respectively. Overall, the rank order of OCs was DDTs>PCBs>hexachlorocyclohexanes (HCHs)>chlordanes (CHLs). The patterns of PCBs showed maximum contribution of tri-CBs (59%). Ratios of individual HCH and DDT analytes contributing to the summed values indicated both recent and past use of these chemicals in the region, depending upon fish species. To assess the associated health risks, carcinogenic and non-carcinogenic risks were calculated through hazard ratios (HRs). For carcinogenic risk, HR was >1 at both 50th and 95th percentile concentrations, suggesting that the daily exposure to OCPs and PCBs yields a lifetime cancer risk of 1 in a million. HR for non-cancerous risk was <1 at both the percentiles, signifying no adverse effect by OCs exposure in native population.

Mass burden and estimated flux of heavy metals in Pakistan coast: sedimentary pollution and eco-toxicological concerns.

Heavy-metal contamination in coastal areas poses a serious threat to aquatic life and public health due to their high toxicity and bio-accumulation potential. In the present study, levels of different heavy metals (Cu, Cd, Cr, Ni, Co, Pb, Zn, and Mn), their spatial distribution, geochemical status, and enrichment indices (Cu, Cd, Cr, Ni, Co, Pb, Zn) were investigated in the sediment samples from 18 coastal sites of Pakistan. The analyses of coastal sediments indicated the presence of heavy metals in order such as Cr > Zn > Cu > Pb > Ni > Mn > Co > Cd. Geo-accumulation index (I geo), enrichment factor (EF), and contamination factor (CF) showed diverse range in heavy-metal enrichment site by site. Pollution load index (PLI) has shown that average pollution load along the entire coastal belt was not significant. Based on the mean effect range medium quotient, coastal sediments of Pakistan had 21% probability of toxicity. The estimated sedimentary load of selected heavy metals was recorded in the range of 0.3-44.7 g/cm(2)/year, while the depositional flux was in the range of 0.07-43.5 t/year. Heavy-metal inventories of 9.8 × 10(2)-3.8 × 10(5) t were estimated in the coastal sediments of Pakistan. The enrichment and contamination factors (EF and CF) suggested significant influence of anthropogenic and industrial activities along the coastal belt of Pakistan.

Influence of taxa, trophic level, and location on bioaccumulation of toxic metals in bird's feathers: a preliminary biomonitoring study using multiple bird species from Pakistan.

Increasing concentrations of heavy metals in the environment and their effects on ecosystems and biota is still an imminent threat, particularly in developing parts of the globe. The aim of the present study was to screen the heavy metal concentrations in multiple bird species across Pakistan and to preliminary evaluate the influence of taxa, trophic level, and geographical location on heavy metal accumulation in various bird species. For this purpose, we measured the concentration of 9 heavy metals (Pb, Cd, Cr, Ni, Co, Cu, Fe, Zn and Mn) in feathers of 48 bird species from different localities in Pakistan. Species exhibited heterogeneous levels of heavy metals in feathers with marked inter and intra specific variations. Mean concentrations of studied metals in feathers followed the trend Fe>Zn>Cu>Pb>Mn>Cr>Ni>Co>Cd. Species belonging to closely related taxa (families) showed comparable metal concentrations in their feathers, inferring potential phylogenetic similarities in metal exposure or accumulation. In general, concentrations of metals were greatest in carnivorous species followed by omnivorous and insectivorous birds, and granivores showing minimal levels (p<0.000). Furthermore, concentrations of metals varied significantly between locations (p<0.000) exhibiting highest concentrations in Punjab province and Baluchistan, probably due to higher industrial and agricultural activity and runoff, respectively. With certain limitation, influence of trophic level, taxonomic affiliation and sampling location of birds on toxic metal accumulation was also statistically corroborated through principal component analysis (PCA). This study highlights that despite restricted emissions, heavy metals persist in the local environment and may pose elevated risks for the studied bird species in Pakistan.

Spatial and interspecific variation of accumulated trace metals between remote and urbane dwelling birds of Pakistan.

The current study was designed to evaluate the hypothesis that birds of urbanized and/or industrialized origin depict higher metal accumulation as compared to remote dwellers. We selected seven representative species from three families (Anatidae, Motacillidae and Sturnidae) at two different locations; Baroghil valley (remote location) and Soan valley (urbanized location) of Pakistan and analyzed the concentrations of 8 metals Pb, Cd, Cr, Ni, Cu, Mn, Fe and Zn in feathers of these species. Feathers from Soan valley which is under higher anthropogenic influence exhibited significantly (P<0.001) higher metal concentrations when compared with the feathers of the same species at Baroghil valley which has negligible anthropogenic input. Terrestrial birds of the Baroghil valley revealed greater metal loads than aquatic birds while at Soan valley it was vice versa. In general, elevated concentrations of metals were recorded in insectivorous species as compared to omnivorous species. Within each location, species belonging to Anatidae and Motacillidae revealed similar metal contamination patterns. Principal component Analysis (PCA) based on correlation matrices depicted a clear tendency of metals towards the species originating from areas with greater pollution load (Soan valley) than relatively undisturbed sites (Baroghil valley) and hence corroborated our hypothesis. The pattern of metal accumulation in feathers of both the locations suggested that there may be a flux of migration between the two regions and/or trans-boundary movement of pollutants/metals, which either singly or synergistically influence the overall metal profile in the studied bird species.

Assessing the relationship and influence of black carbon on distribution status of organochlorines in the coastal sediments from Pakistan.

Levels of total organic carbon (TOC) and black carbon (BC) were determined together with those of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in the selected eighteen coastal sites (n = 285) along the Arabian Sea from Pakistan. Results showed that the total concentration of TOC, BC, ∑OCPs and ∑26PCBs ranged between 0.3 and 2.9% dw, 0.1-0.2% dw, 0.9-110 ng g(-1) dw and 6.2-1200 ng g(-1) dw, respectively. Correlation analysis of BC (r = 0.26-0.89) and TOC (r = 0.06-0.69) revealed a stronger association with studied compounds. The sedimentary depositional fluxes (D) for ∑OCPs and ∑26PCBs were calculated as 1.7 and 4.9 tons yr(-1), respectively. In the coastal belt of Pakistan, sedimentary mass inventories (I) indicated the presence of 13 and 37 metric tons of ∑OCPs and ∑26PCBs, respectively.

Diclofenac residues as the cause of vulture population decline in Pakistan.

The Oriental white-backed vulture (OWBV; Gyps bengalensis) was once one of the most common raptors in the Indian subcontinent. A population decline of >95%, starting in the 1990s, was first noted at Keoladeo National Park, India. Since then, catastrophic declines, also involving Gyps indicus and Gyps tenuirostris, have continued to be reported across the subcontinent. Consequently these vultures are now listed as critically endangered by BirdLife International. In 2000, the Peregrine Fund initiated its Asian Vulture Crisis Project with the Ornithological Society of Pakistan, establishing study sites at 16 OWBV colonies in the Kasur, Khanewal and Muzaffargarh-Layyah Districts of Pakistan to measure mortality at over 2,400 active nest sites. Between 2000 and 2003, high annual adult and subadult mortality (5-86%) and resulting population declines (34-95%) (ref. 5 and M.G., manuscript in preparation) were associated with renal failure and visceral gout. Here, we provide results that directly correlate residues of the anti-inflammatory drug diclofenac with renal failure. Diclofenac residues and renal disease were reproduced experimentally in OWBVs by direct oral exposure and through feeding vultures diclofenac-treated livestock. We propose that residues of veterinary diclofenac are responsible for the OWBV decline.