Assessing the level and sources of Polycyclic Aromatic Hydrocarbons (PAHs) in soil and sediments along Jhelum riverine system of lesser Himalayan region of Pakistan.

Lesser Himalayan Region (LHR) is an important mountain ecosystem which supports a wide range of biodiversity for native flora and fauna. Human population in this region is largely dependent upon local sources for their livelihood. Surface soil (n = 32) and sediment (n = 32) were collected from four different altitudinal ranges of LHR and analyzed for priority Polycyclic Aromatic Hydrocarbons (PAHs) recommended by USEPA. Level, sources and distribution pattern of PAHs were assessed in soil and sediments samples collected from four altitudinal zones in LHR. Total PAHs concentration level of PAHs in soil and sediments ranged from 62.79 to 1080 ng g-1 and 14.54-437.43 ng g-1, respectively. Compositional profile of PAHs in both soil and sediment were dominated by low and medium molecular weight PAHs, ranged from 18.02 to 402.18 ng g-1in soil and 0.32-96.34 ng g-1in sediments. In the context of spatial distribution trend, highest mean concentrations of PAHs in soil were recorded in zone D (sites from the rural region) and for sediments highest concentrations were detected at zone A, which includes dam sites. In all four zones, no altitudinal trend of PAHs in soil and sediments was observed. Source apportionment through receptor modelling by positive matrix factorization (PMF) revealed that local sources such as biomass combustion and vehicular emissions are important sources of PAHs in this region. The prevalence of monsoon atmospheric circulation system in LHR implicated that this region is also influenced by medium and long range atmospheric transportation of PAHs from neighboring countries where potential sources and high level of PAHs has been reported.

Insight into occurrence, profile and spatial distribution of organochlorine pesticides in soils of solid waste dumping sites of Pakistan: Influence of soil properties and implications for environmental fate.

Waste dumping sites are considered as significant disposal pathway for waste contaminants including pesticides. In the present study OCPs were analyzed in soils of waste dumping sites of Pakistan. The mean concentrations of OCPs were in the order: ∑DDTs>∑HCHs>∑Endosulfan>∑HCB>Heptachlor. Order of overall ∑OCPs contamination with respect to location was Lahore>Sukkur>Karachi>Kamoki>Faisalabad>Hyderabad>Losar>Gujrat>Peshawar. Distribution of OCPs in solid waste dumping site was mainly influenced by textural classes, input history and pollution source. Soil texture was the dominant factor for retention of OCPs, whereas TOC and black carbon has not significantly impacted the concentrations of OCPs. Diagnostic ratios indicated the historical input, anaerobic degradation pathway and use of technical mixtures of DDTs in majority of waste dumping sites whereas for HCHs recent as well as past usage of technical mixture was prevalent in most of the areas. Regression analysis revealed a weak positive correlation of OCPs with socioeconomic indices (HDI, Population, waste generation) which is linked with history of use of these contaminants in the respective areas. Forecasted waste generation quantity for the year 2026 showed that waste generation amount will get doubled by the year 2026 suggesting the need properly designed waste management system.

Assessing residual status and spatial variation of current-use pesticides under the influence of environmental factors in major cash crop growing areas of Pakistan.

The status of seven currently used pesticides were assessed under the influence of soil parameters in surface soils of cash crop growing areas of Pakistan. Chlorpyrifos occurred in highest mean concentration (1.18 mg kg-1). Selected pesticides exhibited higher affinity towards both organic carbon and black carbon fractions. The δ13C stable carbon isotopic fraction of inorganic carbon was also used as a tracer and disclosed high retention of total organic carbon in Swat and Swabi sites. Statistical analysis revealed that carbon storage was primarily influenced by altitude and temperature. Soil clay mineral oxides of aluminum and iron positively correlated with organic carbon and selected pesticides (chlorpyrifos and cyprodinil). Soil to plant bio-concentration ratios predicted heightened uptake of azinfos and diazinon in major cash crop bio mass. Occupational risk via soil ingestion expressed no significant threat to the farmer community.

Accounting for water levels and black carbon-inclusive sediment-water partitioning of organochlorines in Lesser Himalaya, Pakistan using two-carbon model.

This study was designed to monitor organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in riverine water of Lesser Himalaya along the altitude. Further, the sediment-water partitioning employing organic carbon and black carbon models were assessed. Results revealed higher water levels of organochlorine pesticides (0.07-41.4 ng L-1) and polychlorinated biphenyls (0.671-84.5 ng L-1) in Lesser Himalayan Region (LHR) of Pakistan. Spatially, elevated levels were observed in the altitudinal zone (737-975 masl) which is influenced by anthropogenic and industrial activities. Sediment-water partitioning of OCPs and PCBs were deduced using field data by employing one-carbon (fOCKOC) and two-carbon Freundlich models (fOCKOC + fBCKBCCWnF-1). Results suggested improved measured vs predicted model concentrations when black carbon was induced in the model and suggested adsorption to be the dominant mechanism in phase partitioning of organochlorines in LHR.

Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along the altitude.

Black carbon (BC) and total organic carbon (TOC) along with their relationship with organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were assessed in Lesser Himalayan Region (LHR) in different altitudinal zones based on anthropogenic influence/source proximity under the scope of this study. Results revealed the concentrations of BC, TOC, OCPs and PCBs varied between 0.3 and 43.5mgg-1, 1.7-65.4mgg-1, 0.59-3.64ngg-1 and 0.01-1.31ngg-1, respectively. Spatial distribution trends have shown higher levels of OCPs and PCBs contamination near populated and urban areas along the altitude. It is implicated that upslope, short and long-range transport and local emission sources contribute to the contamination of different altitudinal zones of LHR. The relationship of BC and TOC with OCPs and PCBs was evaluated using principal component analysis (PCA) and Pearson correlation analysis that indicated higher sorptive influence of BC over TOC in distribution status of organochlorines in LHR. Further research is required to find relationship of BC and TOC in surface riverine sediments, particularly in aquatic systems along the altitude in mountain regions of the world.

Role of black carbon in soil distribution of organochlorines in Lesser Himalayan Region of Pakistan.

Black carbon and total organic carbon (TOC) along with organochlorines (OCs) were analyzed in soils from four sampling zones of Lesser Himalayan Region based on source proximity/anthropogenic influences along the altitude. CTO-375 method was used for BC analysis while OCs were analyzed by GC-MS/MS system. BC and TOC ranged between 0.16-1.77 and 6.8-41.3 mg g-1 while those of OCPs and PCBs ranged between 0.69 and 5.77 and 0.12-2.55 ng g-1, respectively. ∑DDTs were the dominant (87.9%) among OCPs while tri- and tetra- (65.5%) homologue groups among PCBs. Hexa-PCBs, however also showed higher contribution (20.4%) in the region. Source diagnostic ratios of DDE + DDD/DDT (0.1-1.53) indicated both fresh and old input while α-HCH/γ-HCH (0.19-2.49) showed presence of lindane in the region. Higher concentration of OCs were observed in Zone C at altitudinal range of 737-975 masl that are close to the human influences and potential sources of POPs. The results of linear regression analysis revealed potential input of BC in soil distribution of OC concentrations in the region.

Higher atmospheric levels and contribution of black carbon in soil-air partitioning of organochlorines in Lesser Himalaya.

Due to influence of wind patterns (monsoon and westerlies) and anthropogenic activities, lower stretch of Himalaya is at direct exposure to persistent organic pollutants (POPs). Current study was designed to monitor atmospheric concentrations of long lived organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) using polyurethane passive air sampling in the Lesser Himalayan Region (LHR) of Pakistan. Levels of ∑HCHs, ∑DDTs and ∑PCBs were observed in a range between 3 and 210 pg m-3, 0.75-67.1 pg m-3 and 8.49-458 pg m-3, respectively. Though, air mass trajectories over LHR indicated long range transport as atmospheric source input which was further explained by Clausius-Clapeyron plots between ln P and inverse of temperature (1000/T; K) where all OCPs and most of the PCBs have shown insignificant relationship (r2 = 5E-06-0.41; p-value = 0.06-0.995). However, local source emissions and valley transport may also implicate based on spatial distribution and altitudinal patterns. Additionally, soil-air partitioning of organochlorines was assessed using octanol-air partition (KOA) and black carbon-air partition (KBC) based models. Regression results indicated combined influence of both organic matter (r2 = 0.298-0.85) and black carbon (r2 = 0.31-0.86) via absorption and adsorption, respectively in soil-air partitioning of OCs in LHR. This paper sheds light on the atmospheric concentrations of OCs and help in better understanding of the processes involved in fate and transport of organic pollutants in Himalayan region. Further investigations are required to understand the role of carbon moieties in fate and transport of other groups of organic pollutants at higher altitudes of Himalayan region.