Human biomonitoring of trace metals from different altitudinal settings of Pakistan.

Human biomonitoring of toxic trace elements is of critical importance for public health protection. The current study aims to assess the levels of selected trace metals (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn) into paired human nail and hair samples (n = 180 each) from different altitudinal setting along the Indus River, and which were measured by using inductively coupled plasma mass spectrometry (ICP-MS). The human samples (hair and nail) were collected from four different ecological zones of Pakistan which include frozen mountain zone (FMZ), wet mountain zone (WMZ), riverine delta zone (RDZ), and low-lying southern areas (LLZ). Our results showed the following occurrence trends into studied hair samples: higher values (ppm) of Zn (281), Co (0.136), and Mn (5.65) at FMZ; Cr (1.37), Mn (7.83), and Ni (1.22) at WMZ; Co (0.15), Mn (11.89), and Ni (0.99) at RDZ; and Mn (8.99) and Ni (0.90) at LLZ. While in the case of nails, the levels (ppm) of Mn (9.91) at FMZ and Mn (9.38, 24.1, and 12.5), Cr (1.84, 3.87, and 2.33), and Ni (10.69, 8.89, and 12.6) at WMZ, RDZ and LLZ, respectively, showed higher concentration. In general, among the studied trace elements, Mn and Ni in hair/nail samples were consistently higher and exceeded the WHO threshold/published reference values in most of the studied samples (> 50-60%) throughout the Indus basin. Similarly, hair/nail Pb values were also higher in few cases (2-10%) at all studied zones and exceeded the WHO threshold/published reference values. Our area-wise comparisons of studied metals exhibited altitudinal trends for Cd, Cr, Zn, and Mn (p < 0.05), and surprisingly, the values were increasing from south to north (at higher altitudes) and indicative of geogenic sources of the studied toxic elements, except Mn, which was higher at lower floodplain areas. Estimated daily intake (EDI) values showed that food and drinking water had the highest contribution towards Zn, Cu, Mn, and Ni and accumulation at all studied zones. Whereas, dust also acts as the main exposure route for Mn, Co, Cr, and Cd followed by the food, and water.

Assessment and Exposure Analysis of Trace Metals in Different Age Groups of the Male Population in Southern Punjab, Pakistan.

In developing countries, like Pakistan, the pursuit of urbanization and economic development disrupts the delicate ecosystem, resulting in additional biogeochemical emissions of heavy metals into the human habitat and posing significant health risks. The levels of these trace elements in humans remain unknown in areas at higher risk of pollution in Pakistan. In this investigation, selected trace metals including Copper (Cu), Chromium (Cr), Lead (Pb) Cadmium (Cd), Cobalt (Co), Nickel (Ni), and Arsenic (As) were examined in human hair, urine, and nail samples of different age groups from three major cities (Muzaffargarh, Multan, and Vehari) in Punjab province, Pakistan. The results revealed that the mean concentrations (ppm) of Cr (1.1) and Cu (9.1) in hair was highest in Muzaffargarh. In urine samples, the mean concentrations (µg/L) of Co (93), As (79), Cu (69), Cr (56), Ni (49), Cd (45), and Pb (35) were highest in the Multan region, while As (34) and Cr (26) were highest in Vehari. The mean concentrations (ppm) of Ni (9.2), Cr (5.6), and Pb (2.8), in nail samples were highest in Vehari; however, Multan had the highest Cu (28) concentration (ppm). In urine samples, the concentrations of all the studied metals were within permissible limits except for As (34 µg/L) and Cr (26 µg/L) in Vehari. However, in nail samples, the concentrations of Ni in Multan (8.1 ppm), Muzaffargarh (9 ppm), Vehari (9.2 ppm), and Cd (3.69 ppm) in Muzaffargarh exceeded permissible limits. Overall, the concentrations of metals in urine, nail, and hair samples were higher in adults (39-45 age group). Cr, Cu, and Ni revealed significantly higher concentrations of metals in hair and water in Multan, whereas As in water was significantly (p < 0.001) correlated with urinary As in Multan, indicating that the exposure source was region-specific.

Arsenic exposure induces urinary metabolome disruption in Pakistani male population.

Millions of people are at risk of consuming arsenic (As) contaminated drinking water in Pakistan. The current study aimed to investigate urinary arsenic species [iAsIII, iAsV, dimethylarsinic acid (DMA), methylarsonic acid (MMA)] and their potential toxicity biomarkers (based on urinary metabolome) in order to characterize the health effects in general adult male participants (n = 588) exposed to various levels of arsenic in different floodplain areas of Pakistan. The total urinary arsenic concentration (mean; 161 µg/L) of studied participants was lower and/or comparable than those values reported from other highly contaminated regions, but exceeded the Agency for Toxic Substances and Disease Registry (ATSDR) limits. For all the participants, the most excreted species was DMA accounting for 65% of the total arsenic, followed by MMA (20%) and iAs (16%). The percentage of MMA detected in this study was higher than those of previously reported data from other countries. These results suggested that studied population might have high risk of developing arsenic exposure related adverse health outcomes. Furthermore, random forest machine learning algorithm, partial correlation and binary logistic regression analysis were performed to screen the arsenic species-related urinary metabolites. A total of thirty-eight metabolites were extracted from 2776 metabolic features and identified as the potential arsenic toxicity biomarkers. The metabolites were mainly classified into xanthines, purines, and amino acids, which provided the clues linking the arsenic exposure with oxidative stress, one-carbon metabolism, purine metabolism, caffeine metabolism and hormone metabolism. These results would be helpful to develop early health warning system in context of arsenic exposure among the general populations of Pakistan.

Urinary profiles of selected metals and arsenic and their exposure pathway analysis in four large floodplains of Pakistan.

In context of fragile geological conditions and rapid urbanization, element exposure via dietary (food, water) and non-dietary (dust, soil) routes into human population at different land use settings is a major concern in the Indus floodplains (FPs) of Pakistan. In current study, several important trace elements including arsenic (As), chromium (Cr), manganese (Mn), cobalt (Co), cadmium (Cd), nickel (Ni), copper (Cu) and lead (Pb) were analyzed in the paired human urine, food, water and dust samples collected from main FPs of Pakistan. Daily intake estimation and regression analysis were used to evaluate the relationships between internal exposure, exposure routes of studied trace elements and different land use settings. High concentrations of urinary As, Cr, Cu, Mn, and Cd were detected in the general male population of the studied floodplains (FPs). Moreover, the levels (µg/L) of urinary As increased gradually from FP1 (12.8), FP2 (18), FP3 (61) to FP4 (71). Regression analysis showed that As contaminated water was correlated with elevated urinary As concentrations in FP3 and FP4, and water Cr and Mn was significantly associated with urinary Cr and Mn concentrations in FP2. Moreover, the associations of food Mn and urinary Mn were found in FP1. Over all, cumulative estimated daily intake (EDI) values from water, dust and food from all the flood plains showed that Mn had the highest values (6.6, 9.2, 14.4 µg/kg/day) followed by water As (1.98 µg/kg/day), dust Cu (1.5 µg/kg/day) and Pb (1.7 µg/kg/day). Studied floodplains were moderately to highly polluted in terms of studied trace elements (As, Cr, Cu, Mn, and Cd) contamination especially in FP3 and FP4. The results will contribute to improve the knowledge and information on current exposure of Pakistani male adults to the different contaminants.

Assessment of carcinogenic and toxic substances in 'Insunko' herb.

There has emerged a herb in Zambia called 'insunko' which has unknown chemical composition. The use of 'insunko' herb with unknown chemical composition has brought mixed feelings among many Zambians. This study, therefore, aimed to assess the toxic and carcinogenic substances in'insunko' herb. 'Insunko' herb was purchased from Chipata, Lusaka, Mpika, Mwense, Kitwe, and Solwezi. 5 samples were collected from each of these districts and were thoroughly mixed to give 6 consolidated samples (n = 6). Nicotine and, nitrosamines were analysed using UV spectrometer lambda 35 Perkin Elmer while trace metals were analysed using ICP-MS Inductively Coupled Plasma Mass Spectroscopy (Agilent Technologies, Santa Clara, CA, USA). Nicotine, nitrosamines, and trace metals were detected in high concentrations. The concentrations ranged from 3.87 to 9.83 mg/kg for nitrosamines and 10.94-34.01 mg/kg for nicotine. Hazard Indexes for arsenic, cadmium, chromium, manganese, and copper were greater than one (HI > 1). 'Insunko' herb is a potentially toxic and carcinogenic substance because it contains toxic and carcinogenic constituents in high concentrations. These toxic and carcinogenic constituents have been confirmed to cause gastrointestinal disorders, cancers, degenerative, cardiovascular, hematopoietic, neurologic and cognitive problems as well as male infertility.

Health Risk Assessment of Different Heavy Metals Dissolved in Drinking Water.

Water pollution is a major threat to public health worldwide. The health risks of ingesting trace elements in drinking water were assessed in the provinces of Punjab and Khyber Pakhtunkhwa, Pakistan. Eight trace elements were measured in drinking water, using Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and compared with permissible limits established by the World Health Organization (WHO) and the Pakistan Environmental Protection Agency (Pak EPA). In addition, health risk indicators such as the chronic daily intake (CDI) and the health risk index (HRI) were calculated. Our results showed that the concentrations of chromium (Cr), nickel (Ni), and manganese (Mn) were 2593, 1306, and 695 ng/g, respectively, in Lahore and Jhang, while the concentrations of arsenic (As) in Lahore, Vehari, Multan, and Jhang were 51, 50.4, 24, and 22 ng/g, respectively, which were higher than the permissible limits suggested by the WHO. The values of CDI were found to be in the order of Cr > Ni > Mn > Cu > As > Pb > Co > Cd. Similarly, the health risk index (HRI) values exceeded the safe limits (>1) in many cities (eg, Cr and Ni in Lahore and As in Vehari, Jhang, Lahore, and Multan). The aforementioned analysis shows that consumption of trace element-contaminated water poses an emerging health danger to the populations of these localities. Furthermore, inter-metal correlation and principal component analysis (PCA) showed that both anthropogenic and geologic activities were primary sources of drinking water contamination in the investigated areas.

Extensive arsenic contamination in high-pH unconfined aquifers in the Indus Valley.

Arsenic-contaminated aquifers are currently estimated to affect ~150 million people around the world. However, the full extent of the problem remains elusive. This is also the case in Pakistan, where previous studies focused on isolated areas. Using a new data set of nearly 1200 groundwater quality samples throughout Pakistan, we have created state-of-the-art hazard and risk maps of arsenic-contaminated groundwater for thresholds of 10 and 50 µg/liter. Logistic regression analysis was used with 1000 iterations, where surface slope, geology, and soil parameters were major predictor variables. The hazard model indicates that much of the Indus Plain is likely to have elevated arsenic concentrations, although the rest of the country is mostly safe. Unlike other arsenic-contaminated areas of Asia, the arsenic release process in the arid Indus Plain appears to be dominated by elevated-pH dissolution, resulting from alkaline topsoil and extensive irrigation of unconfined aquifers, although pockets of reductive dissolution are also present. We estimate that approximately 50 million to 60 million people use groundwater within the area at risk, with hot spots around Lahore and Hyderabad. This number is alarmingly high and demonstrates the urgent need for verification and testing of all drinking water wells in the Indus Plain, followed by appropriate mitigation measures.