Exposure of polychlorinated naphthalenes (PCNs) to Pakistani populations via non-dietary sources from neglected e-waste hubs: A problem of high health concern.

To date limited information's are available concerning unintentional productions, screening, profiling, and health risks of polychlorinated naphthalenes (PCNs) in ambient environment and occupational environment. Literature reveals that dust is a neglected environmental matrix never measured for PCNs. To our knowledge, this is the first study to investigate the concentrations and health risks of PCNs in indoor dust, air, and blood of major e-waste recycling hubs in Pakistan. Indoor air (n = 125), dust (n = 250), and serum (n = 250) samples were collected from five major e-waste hubs and their vicinity to measure 39 PCN congeners using GC-ECNI-MS. ∑39PCN concentrations in indoor air, dust, and serum (worker > resident > children) samples ranged from 7.0 to 9583 pg/m3, from 0.25 to 697 ng/g, and from 0.15 to 401 pg/g lipid weight, respectively. Predominant PCN congeners in indoor air and dust were tri- and tetra-CNs, while tetra- and penta-CNs were dominant in human serum samples. The higher PCNs contribution was recorded at the recycling units, while the lower was observed at the shops of the major e-waste hubs. Higher contribution of combustion origin CNs in air, dust and human samples showed combustion sources at the major e-waste hubs, while Halowax and Aroclor based technical mixture showed minor contribution in these samples. Mean toxic equivalent (TEQ) concentrations of PCNs were 2.79E+00 pg-TEQ/m3, 1.60E-02 ng-TEQ/g, 8.11E-01 pg-TEQ/g, 7.14E-01 pg-TEQ/g, and 6.37E-01 pg-TEQ/g for indoor air, dust, and serum samples from workers, residents, and children, respectively. In our study, CNs- 66/67 and -73 in indoor air, dust, and human serum were the great contributors to total TEQ concentrations of PCNs. This first base line data directs government and agencies to implement rules, regulation to avoid negative health outcomes and suggests further awareness in regard of provision of proper knowledge to the target population.

Integrated 3D printed heaters for microfluidic applications: Ammonium analysis within environmental water.

A multi-material 3D printed microfluidic reactor with integrated heating is presented, which was applied within a manifold for the colorimetric determination of ammonium in natural waters. Graphene doped polymer was used to provide localised heating when connected to a power source, achieving temperatures of up to 120 °C at 12 V, 0.7 A. An electrically insulating layer of acrylonitrile butadiene styrene (ABS) polymer or a new microdiamond-ABS polymer composite was used as a heater coating. The microdiamond polymer composite provided higher thermal conductivity and uniform heating of the serpentine microreactor which resulted in greater temperature control and accuracy in comparison to pure ABS polymer. The developed heater was then applied and demonstrated using a modified Berthelot reaction for ammonium analysis, in which the microreactor was configured at a predetermined optimised temperature. A 5-fold increase in reaction speed was observed compared to previously reported reaction rates. A simple flow injection analysis set up, comprising the microfluidic heater along with an LED-photodiode based optical detector, was assembled for ammonium analysis. Two river water samples and two blind ammonium standards were analysed and estimated concentrations were compared to concentrations determined using benchtop IC. The highest relative error observed following the analysis of the environmental samples was 11% and for the blind standards was 5%.

Fabrication of Humidity Sensor Using 3D Printable Polymer Composite Containing Boron-Doped Diamonds and LiCl.

Humidity sensing is of significant interest to monitor and control the moisture sensitive environments. Here, we developed a novel 3D printable composite consisting of boron-doped diamond (BDD) (60 wt %) and LiCl (2 wt %) in acrylonitrile butadiene styrene (ABS). SEM analysis of the composite material confirmed the uniform distribution of the BDD and presence of a thin layer of LiCl distributed throughout the matrix. The developed composite material was employed for simple and quick (∼2 min) fabrication of the humidity sensor using low cost fused deposition modeling (FDM) 3D printer. The unique composite material allowed the fabrication of one-piece 3D printed sensor in comparison to traditional multicomponent (e.g., support, sensitive film, and electrodes) humidity sensing devices. The resulting humidity sensor showed excellent sensitivity with up to 125-fold change in resistance for the range of 11-97% relative humidity. The quick response (60 s, n = 3, RSD= 18.7%) and the recovery time (120 s, n = 3, RSD = 16.6%) is attributed to the uniform distribution of the BDD electrode material and strong networking with the LiCl layer distributed throughout the matrix. Long-term stability and repeatability was evaluated, with relative standard deviation of the response of less than 15% obtained over a test period of 14 days. When applied as a sensor for humidity in human breath, the response curves obtained for 12 consecutive breath cycles with post-breath compressed air-drying, showed excellent repeatability and sensitivity, with quick response and recovery (13 s, n = 12, RSD = 15%). The developed 3D printable humidity sensing material was also used to fabricate a customized 3D printed sensor for monitoring the humidity of the N2 supply.

Porogens and porogen selection in the preparation of porous polymer monoliths.

Porogens are key components required for the preparation of porous polymer monoliths for application in separation science. Porogens determine the stability, selectivity, and permeability of polymer monoliths. This review summarizes the role of porogens in the preparation of porous polymer monoliths with a focus on clear understanding of effect of porogens on morphological properties, porosity, surface area, mechanical stability, and permeability of monoliths, particularly targeting the field of separation science. This review also includes the use of different types of porogens with the focus on various approaches used to set criteria for their systematic selection, including porogen-free techniques recently used for synthesis of porous monoliths. It discusses the current state-of-the-art applications of porogens in column preparation as well as where the future developments in this field may be directed.

Three-Dimensional Printing of Abrasive, Hard, and Thermally Conductive Synthetic Microdiamond-Polymer Composite Using Low-Cost Fused Deposition Modeling Printer.

A relative lack of printable materials with tailored functional properties limits the applicability of three-dimensional (3D) printing. In this work, a diamond-acrylonitrile butadiene styrene (ABS) composite filament for use in 3D printing was created through incorporation of high-pressure and high-temperature (HPHT) synthetic microdiamonds as a filler. Homogenously distributed diamond composite filaments, containing either 37.5 or 60 wt % microdiamonds, were formed through preblending the diamond powder with ABS, followed by subsequent multiple fiber extrusions. The thermal conductivity of the ABS base material increased from 0.17 to 0.94 W/(m·K), more than five-fold following incorporation of the microdiamonds. The elastic modulus for the 60 wt % microdiamond containing composite material increased by 41.9% with respect to pure ABS, from 1050 to 1490 MPa. The hydrophilicity also increased by 32%. A low-cost fused deposition modeling printer was customized to handle the highly abrasive composite filament by replacing the conventional (stainless-steel) filament feeding gear with a harder titanium gear. To demonstrate improved thermal performance of 3D printed devices using the new composite filament, a number of composite heat sinks were printed and characterized. Heat dissipation measurements demonstrated that 3D printed heat sinks containing 60 wt % diamond increased the thermal dissipation by 42%.

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.

Enhanced physicochemical properties of polydimethylsiloxane based microfluidic devices and thin films by incorporating synthetic micro-diamond.

Synthetic micro-diamond-polydimethylsiloxane (PDMS) composite microfluidic chips and thin films were produced using indirect 3D printing and spin coating fabrication techniques. Microfluidic chips containing up to 60 wt% micro-diamond were successfully cast and bonded. Physicochemical properties, including the dispersion pattern, hydrophobicity, chemical structure, elasticity and thermal characteristics of both chip and films were investigated. Scanning electron microscopy indicated that the micro-diamond particles were embedded and interconnected within the bulk material of the cast microfluidic chip, whereas in the case of thin films their increased presence at the polymer surface resulted in a reduced hydrophobicity of the composite. The elastic modulus increased from 1.28 for a PDMS control, to 4.42 MPa for the 60 wt% composite, along with a three-fold increase in thermal conductivity, from 0.15 to 0.45 W m-1 K-1. Within the fluidic chips, micro-diamond incorporation enhanced heat dissipation by efficient transfer of heat from within the channels to the surrounding substrate. At a flow rate of 1000 µL/min, the gradient achieved for the 60 wt% composite chip equalled a 9.8 °C drop across a 3 cm long channel, more than twice that observed with the PDMS control chip.

Pesticides contaminated dust exposure, risk diagnosis and exposure markers in occupational and residential settings of Lahore, Pakistan.

There are few studies documenting the dust loaded with pesticides as a potential non-dietary exposure source for occupational worker and populations living near agricultural farms and pesticides formulation plants. In present study we have evaluated the pesticide concentration in dust from potential sites and relevant health risk from dust ingestion. Furthermore, the effect of currently used pesticides was investigated on blood and urine parameters of subjects: farmer, factory worker, urban resident and rural resident and controlled subjects with presumably different levels of exposure. The urinary metabolites (TCPY and IMPY) were quantified as biomarkers of exposure to chlorpyrifos and diazinon in relation with biomarkers of effect including BuChE, LH, FSH, testosterone and oxidative stress. Results showed that chlorpyrifos and diazinon were present in higher concentration in dust and posed a high health risk to exposed subjects. The mean SOD value was high among the farmer (3048U/g Hb) followed by factory worker (1677.6U/g Hb). The urinary biomarkers - TCPY and IMPY- were found higher in exposed subjects as compared to control. Furthermore, testosterone was found in higher concentration in factory worker than control (12.63ng/ml vs 4.61ng/ml respectively). A decreased BuChE activity was noticed in occupational group and significant differences were observed in control verses exposed subjects. The PCA analysis evidenced the impact of pesticides on exposure biomarkers and male reproductive hormones. The study suggests that dust contaminated with pesticides engenders significant health risk particularly related to the nervous and endocrine system, not only for occupational workers exposed to direct ingestion but also for nearby residential community. Succinctly putting: Pesticides loaded dust in the city of Lahore, being a high priority concern for the government of Pakistan, demands to be addressed.

Self-sterilized composite membranes of cellulose acetate/polyethylene glycol for water desalination.

Cellulose acetate/Polyethylene glycol-600 composite membranes were fabricated by two step phase inversion procedure and modified by in-situ reduction of silver nitrate. FTIR spectra demonstrated the existence of functional groups for bonding of silver with oxygen at 370cm(-1), 535cm(-1). The XRD diffractogram indicates characteristic peaks at 2θ values of 38.10°, 44.30°, 64.40°, and 77.30° which confirm the successful incorporation of silver within matrix of composite membranes. The morphology of composite membranes with appearances of spongy voids was exemplified from the scanning electron microscope. The atomic force microscopy was used to determine the increase in the surface roughness of the membranes. The increase in hydrophilicity, measured through contact angle, is rendered to the embedment of silver. The modification of membranes increased the flux from 0.80 to 0.95L/hr.m(2). The resulting membranes have outstanding ability to fight against gram negative Escherichia Coli and Bacillus Sabtilus. The novel cellulose acetate/polyethylene glycol membranes customized with silver have paved the path for evolution of axenic membranes.

3D printed microfluidic devices: enablers and barriers.

3D printing has the potential to significantly change the field of microfluidics. The ability to fabricate a complete microfluidic device in a single step from a computer model has obvious attractions, but it is the ability to create truly three dimensional structures that will provide new microfluidic capability that is challenging, if not impossible to make with existing approaches. This critical review covers the current state of 3D printing for microfluidics, focusing on the four most frequently used printing approaches: inkjet (i3DP), stereolithography (SLA), two photon polymerisation (2PP) and extrusion printing (focusing on fused deposition modeling). It discusses current achievements and limitations, and opportunities for advancement to reach 3D printing's full potential.

Enrichment, geo-accumulation and risk surveillance of toxic metals for different environmental compartments from Mehmood Booti dumping site, Lahore city, Pakistan.

The present study was designed to probe the levels of heavy metals (Cd, Pb, Cr, Mn, Cu, Ni, Zn and Fe) for different environmental matrices (ground water, wastewater, sediment, soil, dust and leachates). Impact of solid waste dumping site on nearby human population has also been assessed. The results revealed that concentration of Pb, Fe, Cd, Mn and Cu surpassed the permissible limits of World Health Organization (WHO) and US Environmental Protection Agency (USEPA) in water, soil, sediments, while aforesaid metals in wastewater were above the National Environmental Quality Standards (NEQS). Our results for enrichment factor (EF) and geo-accumulation (I(geo)) values revealed that soils and sediments were contaminated with Cd, Pb, Ni and Mn. The Cd content caused a considerably high potential ecological risk (E(r)(i) ≥ 320) in soil and sediments. Pb and Cd caused high health risk (HR > 1) to local residents via dust and drinking water intake. Potential cancer risk for Pb was higher than USEPA standard values (1.0E-06-1.0E-04) through water intake. The Mehmood Booti dumping site is a potential source of toxic pollutants contamination to the surrounding population. It is recommended to take proper actions for its management to resolve this issue.

Human health risk from organ-specific accumulation of toxic metals and response of antioxidants in edible fish species from Chenab River, Pakistan.

In the current study, the bioaccumulation of essential and nonessential metals and related antioxidant activity were analyzed in three organs (muscle, gills, and liver) of herbivorous (HF) and carnivorous (CF) edible fish of Chenab River. The comparative analysis revealed a more heterogeneous accumulation of metals in the muscles of HF fish than that of CF fish [chromium (Cr, 3.4 µg g(-1)), cobalt (Co, 1.7 µg g(-1)), copper (Cu, 3 µg g(-1)), and iron (Fe, 45 µg g(-1)) versus Cr (1.3 µg g(-1)), Co (0.1 µg g(-1)), Cu (1.1 µg g(-1)), and Fe (33 µg g(-1)), respectively, P<0.001]. These results implied an organ-specific accumulation of metals at different trophic levels. According to logistic regression analysis, the bioaccumulation of metals had marked differences in HF and CF. The antioxidant activity was significantly related to the tissue type and the metals to which the organs are exposed to. The liver of CF fish had a higher activity of antioxidant superoxide dismutase (SOD), catalase (CAT), glutathione (GSH), and lipid peroxidase (LPO) than that of HF (P<0.05). LPO and guaiacol peroxidase (POD) in both groups were associated with a number of metals, but in HF, cadmium (Cd), Cr, Pb, and Zn were more related with the LPO and SOD activities. Moreover, Cd, Co, Fe, Pb, Ni, Cu, and Zn were above the permissible limits set by various agencies. In numerous cases, our results were even higher than those previously reported in the literature. The results provide an insight into the pollution pattern of Chenab River. These results may be helpful in the future to identify biomarkers of exposure in aquatic organisms.

Health risk from As contaminated fish consumption by population living around River Chenab, Pakistan.

We analyzed six edible fish species (Securicola gora; Cirrhinus reba; Rita rita; Sperata sarvari; Culpisoma naziri and Labeo kalbasu) to evaluation As contamination. These species were caught from the River Chenab of Pakistan. The aim of this study was to determine the concentration of arsenic (As) and the antioxidant response in the muscle, liver and gills. The sampling sites were divided into agricultural, industrial and urban land uses. Although, the highest concentration of As, and the antioxidant activity was found in the liver, but the muscles also had a high concentration of As than that of gills. The range of As detected in these tissues was in the following order: Liver (0.009-3.95µgg(-1))>muscles (0.006-3.5µgg(-1))>gills (0.002-2.96µgg(-1)). Furthermore, the R. rita showed the highest concentration of As (2.18µgg(-1)) followed by S. sarvari (1.98µgg(-1)). The median concentrations of As, in the liver and muscles were also above the FAO/WHO, EPA permissible limits. The LPO activity was significantly related to As, which showed a possibility of cell membrane damage in these species. The human health risk assessment revealed that higher than normal concentration of As in muscle was particularly hazardous for the younger population.

Neurofibromatosis-1 with intraventricular haemorrhage and pectus excavatum.

This case report describes the occurrence of intraventricular haemorrhage in a teenage boy, who was later found to have neurofibromatosis-1, cerebral vascular disease and pectus excavatum.