Molecular signatures and formation mechanisms of water-soluble chromophores in particulate matter from Karachi in Pakistan.

Excitation-emission matrix (EEM) fluorescence spectroscopy is a widely-used method for characterizing the chemical components of brown carbon (BrC). However, the molecular basics and formation mechanisms of chromophores, which are decomposed by parallel factor (PARAFAC) analysis, are not yet fully understood. In this study, we characterized the water-soluble organic carbon (WSOC) in aerosols collected from Karachi, Pakistan, using EEM spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We identified three PARAFAC components, including two humic-like components (C1 and C2) and one phenolic-like species (C3). We determined the molecular families associated with each component by performing Spearman correlation analysis between FT-ICR MS peaks and PARAFAC component intensities. We found that the C1 and C2 components were associated with nitrogen-enriched compounds, where C2 with the longest emission wavelength exhibited a higher level of aromaticity, N content, and oxygenation than C1. The C3 associated formulas have fewer nitrogen-containing species, a lower unsaturation degree, and a lower oxidation state. An oxidation pathway was identified as an important process in the formation of C1 and C2 components at the molecular level, particularly for the assigned CHON compounds associated with the gas-phase oxidation process, despite their diverse precursor types. Numerous C2 formulas were found in the "potential BrC" region and overlapped with the BrC-associated formulas. It can be inferred that the compounds that fluoresce C2 contributed considerably to the light absorption of BrC. These findings are essential for future studies utilizing the EEM-PARAFAC method to explore the sources, processes, and compositions of atmospheric BrC.

Gaseous elemental mercury emissions from informal E-Waste recycling facilities in Pakistan.

Detrimental effects of mercury (Hg) on ecosystems and human health have been well-documented. Whereas emissions of gaseous elemental mercury (GEM) from e-waste recycling have been reported in developed countries, much less is known about the situation in the Global South. Using a total of 132 passive air samplers, seasonally resolved concentrations of GEM in air were measured continuously at 32 informal e-waste recycling facilities and background location in Pakistan for a period of one year between September 2020 and December 2021. Annual average GEM concentrations at the studied locations ranged from 1.8 to 92 ng m-3. Among the studied cities, higher concentrations were measured in Karachi (mean ± s.d: 17 ± 22, range: 4.2-92 ng m-3), Lahore (16 ± 4.2, 8.2-22 ng m-3) and Peshawar (15 ± 17, 4.9-80 ng m-3), while lower levels were measured in Hyderabad (6.9 ± 6.2, 3.1-25 ng m-3), consistent with a higher rate of informal recycling activities in metropolitan areas. Seasonally, higher GEM levels occurred during autumn (15 ± 16: 3.3-92 ng m-3) and summer (13 ± 8.7: 1.8-80 ng m-3) than in winter (12 ± 8.4: 2.5-49 ng m-3) and spring (9.2 ± 7.3: 1.8-80 ng m-3), possibly reflecting enhanced volatilization at higher temperatures and/or varying magnitude of recycling operations in different seasons. Policies and strict regulations related to e-waste management should be developed and implemented urgently in the country.

Investigating the degradation behavior of Cypermethrin (CYP) and Chlorpyrifos (CPP) in peach orchard soils using organic/inorganic amendments.

Reducing toxic effects of pesticide residues in agricultural soils through organic amendments is an eco-friendly technique. Cypermethrin (CYP) and Chlorpyrifos (CPP) are widely used pesticides in peach growing orchards in Swat valley of Pakistan. The aim of the current study was to investigate the degradation behavior of CYP and CPP in soil by the application of different combination of organic/inorganic amendments. A total of 36 soil samples were used in the current incubation study which was collected from 4 peach orchards in district Swat, Khyber Pakhtunkhwa (KPK), Pakistan. Different amendments including urea, farm yard manure (FYM) and saprofil were applied alone and in various combinations. The initial concentrations of CYP and CPP in the tested soil was range from 0.94 to 4.8 mg kg-1 and 0.024 to 4.12 to mg kg-1. Soil samples were taken at 5, 15, 30 and 45 days after exposure to different treatments. The extraction of pesticides from soils was done through quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method. Soils amended with urea, FYM and saprofil individually and in combinations significantly reduced the concentrations of CYP and CPP. However, the concentration of CYP (24.6) and CPP (27.0) in soil showed higher reduction through the application of FYM. While the concentrations of CYP and CPP were declined with the 5, 15, 30 and 45 days intervals, however, reduction at day 30 and 45 was faster for CYP (16.7 to 8.46) than CPP (20.2 to 12.3). At day 5 and 15, the CYP (42.5 to 30.7) was slightly lower than CPP (42.9 to 32.7).The highest half-life value (t ½) of CYP was in control treatment (32 days) and the shortest was soil amended with FYM (18.6 days). While the longest half-life value (t ½) of CPP was maximum in control treatment (42 days) and the minimum was in FYM (22 days). Based on our findings, it was concluded that soil application of FYM is recommended for the degradation of CYP and CPP.

Human Health Risk Assessment by Dietary Intake and Spatial Distribution Pattern of Polybrominated Diphenyl Ethers and Dechloran Plus from Selected Cities of Pakistan.

A class of intractable bio accumulative halogenated compounds polybrominated diphenyl ethers (PBDEs) was studied. Specifically, PBDEs and dechloran plus (DP) contamination in wheat and the assaulted environment-agricultural soil and dust-from metropolitan cities of Pakistan was the focus. The exposure of brominated flame retardants (BFRs) to humans, their probable toxicological impact on health, source apportionment, and the spatial tendency of BFRs were studied. Chromatographic analysis was performed, and concentrations (ng g-1) of ΣPBDE and ΣDP in soil, dust, and cereal crops were estimated in a range from 0.63 to 31.70 n.d. to 6.32 and n.d. to 3.47, respectively, and 0.11 to 7.05, n.d. to 4.56 and 0.05 to 4.95, respectively. Data analysis of source apportionment reflected that the existence of solid and e-waste sites, long-range transport, urban and industrial fraction can be the potential source of PBDE and DP pollution. Moreover, potential hazardous risks to human health across the study area via the dietary intake of cereal foods were deemed trifling, and were gauged on the basis of existing toxicological data.

Screening of atmospheric short- and medium-chain chlorinated paraffins in India and Pakistan using polyurethane foam based passive air sampler.

Production and use of chlorinated paraffins (CPs) have been increasing in India. Distribution of CPs in the area and vicinity have become a great concern due to their persistency and toxicity. Polyurethane foam based passive air samplers (PUF-PAS) was deployed in order to screen the presence of short- and medium- chain chlorinated paraffins (SCCPs and MCCPs) in the outdoor atmosphere at many sites in India (in winter 2006) and Pakistan (in winter 2011). Concentrations of SCCPs and MCCPs ranged from not detected (ND) to 47.4 and 0 to 38.2 ng m(-3) with means of 8.11 and 4.83 ng m(-3), respectively. Indian concentrations showed higher average levels of both SCCPs and MCCPs India (10.2 ng m(-3) and 3.62 ng m(-3)than the samples from Pakistan (5.13 ng m(-3) and 4.21 ng m(-3)). Relative abundance patterns of carbon number are C10 > C11 > C12 ∼ C13 for SCCPs and C14 > C15 > C16 C17 for MCCP with similarity to the profiles of samples from China, the biggest CPs producer in the world. Principal Component Analysis suggested that detected SCCPs and MCCPs in this study originated from the same emission source.