Influence of agro-wastes derived biochar and their composite on reducing the mobility of toxic heavy metals and their bioavailability in industrial contaminated soils.

The agro-waste derived valuable products are prime interest for effective management of toxic heavy metals (THMs). The present study investigated the efficacy of biochars (BCs) on immobilization of THMs (Cr, Zn, Pb, Cu, Ni and Cd), bioaccumulation and health risk. Agro-wastes derived BCs including wheat straw biochar (WSB), orange peel biochar (OPB), rice husk biochar (RHB) and their composite biochar (CB) were applied in industrial contaminated soil (ICS) at 1% and 3% amendments rates. All the BCs significantly decreased the bioavailable THMs and significantly (p < 0.001) reduced bioaccumulation at 3% application with highest efficiency for CB followed by OPB, WSB and RHB as compared to control treatment. The bioaccumulation factor (BAF), concentration index (CI) and ecological risk were decreased with all BCs. The hazard quotient (HQ) and hazard index (HI) of all THMs were <1, except Cd, while carcer risk (CR) and total cancer risk index (TCRI) were decreased through all BCs. The overall results depicted that CB at 3% application rate showed higher efficacy to reduce significantly (p < 0.001) the THMs uptake and reduced health risk. Hence, the present study suggests that the composite of BCs prepared from agro-wastes is eco-friendly amendment to reduce THMs in ICS and minimize its subsequent uptake in vegetables.

The present study has a scientific research scope, based on reduction of bioavailability and bioaccumulation of toxic heavy metals (THMs) by the addition of biochars derived from agro-wastes and their composite biochar (CB), thereby decreasing the potential health risk. Limited study has been conducted, especially on the impact of CB in THMs-contaminated soil. This study could fill the scientific research gap and provides useful information for mitigation of THMs present in contaminated soil, which could be followed by the Environmental Protection Agency, Ministry of Agriculture and farmers in degraded lands.

Contamination level, source identification and health risk assessment of potentially toxic elements in drinking water sources of mining and non-mining areas of Khyber Pakhtunkhwa, Pakistan.

Accelerated mining activities have increased water contamination with potentially toxic elements (PTEs) and their associated human health risk in developing countries. The current study investigated the distribution of PTEs, their potential sources and health risk assessment in both ground and surface water sources in mining and non-mining areas of Khyber Pakhtunkhwa, Pakistan. Water samples (n = 150) were taken from selected sites and were analyzed for six PTEs (Ni, Cr, Zn, Cu, Pb and Mn). Among PTEs, Cr showed a high mean concentration (497) µg L-1, followed by Zn (414) µg L-1 in the mining area, while Zn showed the lowest mean value (4.44) µg L-1 in non-mining areas. Elevated concentrations of Ni, Cr and a moderate level of Pb in ground and surface water of Mohmand District exceeded the permissible limits set by WHO. Multivariate statistical analyses showed that the pollution sources of PTEs were mainly from mafic-ultramafic rocks, acid mine drainage, open dumping of mine wastes and mine tailings. The hazard quotient (HQ) was the highest for children relative to that for adults, but not higher than the USEPA limits. The hazard index (HI) for ingestions of all selected PTEs was lower than the threshold value (HIing < 1), except for Mohmand District, which showed a value of HI >1 in mining areas through ingestion. Moreover, the carcinogenic risk (CR) values exceeded the threshold limits for Ni and Cr set by the USEPA (1.0E-04-1.0E-06). In order to protect the drinking water sources of the study areas from further contamination, management techniques and policy for mining operations need to be implemented.

Occurrence and Distribution of Heavy Metals in Mining Degraded Soil and Medicinal Plants: A Case Study of Pb/Zn Sulfide Terrain Northern Areas, Pakistan.

Mining activities have serious environmental impacts, thus releasing heavy metals (HMs) such as cadmium (Cd), lead (Pb), chromium (Cr), zinc (Zn) and nickel (Ni) into the surrounding environment. The current paper investigated the impacts of mining activities of Pb-Zn sulfide on soil and medicinal plants. Hence, soil samples (n = 36) and medicinal plants (n = 36) samples were collected, acid extracted and were analyzed through Inductively Coupled Plasma Mass Spectrometry (ICP-MS) for HMs quantification. Our results showed that mineralized zones showed high HMs enrichment levels as compared to non-mineralized zones. Various Indices for HMs assessment revealed that the contaminated soil of the study area had low to extreme level. The mean concentrations of HMs in mining degraded soil and medicinal plants were significantly higher (p ≤ 0.01) and were found in order of Zn > Pb > Cr > Ni > Cd and Cr > Zn > Pb > Ni > Cd respectively. Similarly, some widely consumable medicinal plants showed good metal accumulation for Cd, Cr and Pb i.e., 3.57 mg kg1, 350 mg kg-1 and 335 mg kg-1 in C. sativa, while 5.9 mg kg-1, 276.9 mg kg-1 and 188.7 mg kg-1 in R. hestatus respectively. Hence, the present study recommended that medicinal plants grown in mining areas should be analyzed for HMs concentration before consumption.

Occurrence of N-nitrosamines and their precursors in the middle and lower reaches of Yangtze River water.

The presence of some types of N-nitrosamines in water bodies is of great concern worldwide due to their carcinogenic risks and harmful mutagenic effects on human health. In the present study, eight N-nitrosamines and their formation potentials (FPs) were primarily investigated in Yangtze River surface water to evaluate their spatial distribution, mass loads, and ecological risks. The results showed that of the eight N-nitrosamines investigated, NDMA (<1.5-17 ng/L), NDEA (<1.4-9.5 ng/L), NDPA (1.0 ng/L), NMOR (<1.0-1.3 ng/L), NPIP (<2.1-3.7 ng/L), and NDBA (<3.6-30 ng/L) were detected. The FPs of NDMA (<27-130 ng/L), NDEA (<0.9-2.3 ng/L), NDPA (<1.2-1.9 ng/L), NPYR (<1.4-2.9 ng/L), NMOR (<1.0 ng/L), and NDBA (<1.1-14 ng/L) were significantly identified. NDBA was predominantly observed in surface water, while NDMA was noticeably detected in chloraminated water samples. It was estimated that approximately 5.4 t/y of N-nitrosamines were carried by the Yangtze River to the East China Sea, whereas the input flux of N-nitrosamine precursors was estimated to be approximately 69.5 t/y. Spatial variations were observed due to the input of N-nitrosamines from the upstream dams and lakes. The origin of N-nitrosamine precursors was not associated with the presence of sediment in river water. NDEA could be introduced into river water by the discharge of wastewater. NDBA and its precursors could originate from industrial and aquaculture activities. NDMA and its precursors could result from both of the aforementioned sources. Moreover, the wastewater discharge from small cities, pH value, wastewater treatment ratio, and dilution could be the key factors that influence the occurrence of N-nitrosamines along the Yangtze River. More attention should be paid to the cancer risks posed by N-nitrosamines. The ecological risks posed by N-nitrosamines in the Yangtze River can be ignored.

Minimizing the risk to human health due to the ingestion of arsenic and toxic metals in vegetables by the application of biochar, farmyard manure and peat moss.

Mining activity releases toxic metals (TMs) into the soil ecosystem and creates serious problems for the environment and human beings due to their adverse eco-toxilogical impacts. Currently, several remediation techniques can be used to immobilize TMs within contaminated soil. The present study focuses on the application of different organic amendments biochar (B), farmyard manure (FYM) and peat moss (PTM) - at different application rates (1%, 2% and 5%) in mining-impacted agricultural soil to immobilize TMs (Ni, Cr, As, Zn, Cd and Pb) and minimize their bioaccumulation in pea (Pisum sativum) and chili (Capsicum annuum) and the associated human health risk. Among the organic amendments, the treatments at the 5% application rate of B, FYM and PTM significantly (p ≤ 0.001) reduced the bioavailability of TM concentrations in amended soil and increased pea and chili plants' and fruits' biomasses when compared with the control. Moreover, risk assessments showed that B, FYM and PTM decreased the daily intake and health risk associated with the consumption of vegetables effectively for individual TMs compared with the control. The highest application rate of 5% significantly (p ≤ 0.001) reduced the average daily intake of TMs and their health risk, as compared to 1% and 2%, for both adults and children. The health risk index (HRI ˂ 1) values were lower (and within safety limits) for adults and children consuming vegetables grown on organic-amended soils. The results indicate that the B5% treatment of this mining-impacted agricultural soil was the most efficient at increasing plant and fruit biomasses and reducing the bioavailability, bioaccumulation and daily intake of TMs and their potential health risk through consumption of vegetables such as pea and chili, as compared to FYM, PTM and the control treatment.

Integrated Approach to Hydrogeochemical Assessment of Groundwater Quality in Major Industrial Zone of Punjab, Pakistan.

Groundwater contamination with arsenic (As) is a significant concern in Pakistan's Punjab Province. This study analyzed 69 groundwater samples from Faisalabad, Gujranwala, Lahore, and Multan to understand hydrogeochemistry, health impacts, contamination sources, and drinking suitability. Results revealed varying as concentrations across districts, with distinctive cation and anion orders. Faisalabad exhibited Na+ > Mg2+ > Ca2+ > K+ > Fe2+ for cations and SO42- > Cl- > HCO3- > NO3- > F- for anions. Gujranwala showed Na+ > Ca2+ > Mg2+ > K+ for cations and HCO3- > SO42- > Cl- > NO3- > F- for anions. In Lahore, demonstrated: Na+ > Ca2+ > Mg2+ > Fe > K+ for cations and HCO3- > SO42- > Cl- > NO3- > F- for anions. Multan indicated K+ > Ca2+ > Mg2+ > Na+ > Fe for cations and HCO3- > SO42- > Cl- > F- > NO3- ) for anions. Hydrochemical facies were identified as CaHCO3 and CaMgCl types. Principal Component Analysis (PCA), highlighted the influence of natural processes and human activities on groundwater pollution. Water Quality Index (WQI) result reveal that most samples met water quality standards. The carcinogenic risk values for children exceeded permissible limits in all districts, emphasizing a significant cancer risk. The study highlights the need for rigorous monitoring to mitigate (As) contamination and protect public health from associated hazards.

Arsenic Contamination, Water Toxicity, Source Apportionment, and Potential Health Risk in Groundwater of Jhelum Basin, Punjab, Pakistan.

Potable groundwater (GW) contamination through arsenic (As) is a commonly reported environmental issue in Pakistan. In order to examine the groundwater quality for As contamination, its geochemical behavior, and other physicochemical parameters, 69 samples from various groundwater sources were collected from the mining area of Pind Dadan Khan, Punjab, Pakistan. The results showed the concentration of elevated As, its source of mobilization, and linked public health risk. Arsenic detected in the groundwater samples varied from 0.5 to 100 µg/L, with an average value of 21.38 µg/L. Forty-two samples were beyond the acceptable limit of 10 µg/L of the WHO for drinking purposes. The statistical summary showed that the groundwater cation concentration was in decreasing order such as Na+ > Ca2+ > Mg2+ > K+, while anions were as follows: HCO3- > SO42- > Cl- > NO3-. Hydrochemical facies results depicted that groundwater samples belong to CaHCO3 type. Rock-water interactions control the hydrochemistry of groundwater. Saturation indices' results indicated the saturation of the groundwater sources for CO3 minerals due to their positive SI values. Such minerals include aragonite, calcite, dolomite, and fluorite. The principal component analysis (PCA) findings possess a total variability of 77.36% suggesting the anthropogenic and geogenic contributing sources of contaminant. The results of the Exposure-health-risk-assessment model for measuring As reveal significant potential carcinogenic risk exceeding the threshold level (value > 10-4) and HQ level (value > 1.0).

Groundwater fluoride and nitrate contamination and associated human health risk assessment in South Punjab, Pakistan.

Consumption of high fluoride (F-) and nitrate (NO3-) containing water may pose serious health hazards. One hundred sixty-one groundwater samples were collected from drinking wells in Khushab district, Punjab Province, Pakistan, to determine the causes of elevated F- and NO3- concentrations, and to estimate the human health risks posed by groundwater contamination. The results showed pH of the groundwater samples ranged from slightly neutral to alkaline, and Na+ and HCO3- ions dominated the groundwater. Piper diagram and bivariate plots indicated that the key factors regulating groundwater hydrochemistry were weathering of silicates, dissolution of evaporates, evaporation, cation exchange, and anthropogenic activities. The F- content of groundwater ranged from 0.06 to 7.9 mg/L, and 25.46% of groundwater samples contained high-level fluoride concentration (F- > 1.5 mg/L), which exceeds the (WHO Guidelines for drinking-water quality: incorporating the first and second addenda, WHO, Geneva, 2022) guidelines of drinking-water quality. Inverse geochemical modeling indicates that weathering and dissolution of fluoride-rich minerals were the primary causes of F- in groundwater. High F- can be attributed to low concentration of calcium-containing minerals along the flow path. The concentrations of NO3- in groundwater varied from 0.1 to 70 mg/L; some samples are slightly exceeding the (WHO Guidelines for drinking-water quality: incorporating the first and second addenda, WHO, Geneva, 2022) guidelines for drinking-water quality. Elevated NO3- content was attributed to the anthropogenic activities revealed by PCA analysis. The high levels of nitrates found in the study region are a result of various human-caused factors, including leaks from septic systems, the use of nitrogen-rich fertilizers, and waste from households, farming operations, and livestock. The hazard quotient (HQ) and total hazard index (THI) of F- and NO3- showed high non-carcinogenic risk (> 1) via groundwater consumption, demonstrating a high potential risk to the local population. This study is significant because it is the most comprehensive examination of water quality, groundwater hydrogeochemistry, and health risk assessment in the Khushab district to date, and it will serve as a baseline for future studies. Some sustainable measures are urgent to reduce the F- and NO3- content in the groundwater.

New insights into the migration, distribution and accumulation of micro-plastic in marine environment: A critical mechanism review.

Microplastics (MPs) are widely distributed in the marine environment, posing a significant threat to marine biota. The contribution of anthropogenic and terrestrial sources to the aquatic ecosystem has led to an increase in MPs findings, and their abundance in aquatic biota has been reported to be of concern. MPs are formed mainly via photo degradation of macroplastics (large plastic debris), and their release into the environment is a result of the degradation of additives. Eco-toxicological risks are increasing for marine organisms, due to the ingestion of MPs, which cause damage to gastrointestinal (GI) tracts and stomach. Plastics with a size <5 mm are considered MPs, and they are commonly identified by Raman spectroscopy, Fourier transfer infrared (FTIR) spectroscopy, and Laser direct infrared (LDIR). The size, density and additives are the main factors influencing the abundance and bioavailability of MPs. The most abundant type of MPs found in fishes are fiber, polystyrenes, and fragments. These microscale pellets cause physiological stress and growth deformities by targeting the GI tracts of fishes and other biota. Approximately 80% MPs come from terrestrial sources, either primary, generated during different products such as skin care products, tires production and the use of MPs as carrier for pharmaceutical products, or secondary plastics, disposed of near coastal areas and water bodies. The issue of MPs and their potential effects on the marine ecosystem require proper attention. Therefore, this study conducted an extensive literature review on assessing MPs levels in fishes, sediments, seawater, their sources, and effects on marine biota (especially on fishes), chemo-physical behavior and the techniques used for their identification.

Integrated approach to hydrogeochemical appraisal of groundwater quality concerning arsenic contamination and its suitability analysis for drinking purposes using water quality index.

Arsenic (As), contamination in drinking groundwater resources is commonly environmental problem in many developing countries including Pakistan, with significant human health risk reports. In order to examine the groundwater quality concerning As contamination, its geochemical behavior along with physicochemical parameters, 42 samples were collected from community tube wells from District Bahawalpur, Punjab, Pakistan. The results showed the concentration of elevated As, its source of mobilization, and associated public health risk. The As concentration detected in groundwater samples varied from 0.12 to 104 µg/L with an average value of 34.7 µg/L. Among 42 groundwater samples, 27 samples were beyond the permitted limit of 10 µg/L recommended by World Health Organization (WHO), for drinking purposes. Statistical analysis result show that the groundwater cations values are in decreasing order such as: Na+ > Mg2+ > Ca2+ > K+, while anions were HCO3- > SO42- > Cl- > NO3-. Hydrochemical facies result depict that the groundwater samples of the study area, 14 samples belong to CaHCO3 type, 5 samples belong to NaCl type, 20 samples belong to Mixed CaMgCl type, and 3 samples belong to CaCl2 type. It can be accredited due to weathering and recharge mechanism, evaporation processes, and reverse ion exchange. Gibbs diagram shows that rock water interaction controls the hydrochemistry of groundwater resources of the study area. Saturation Index (SI) result indicated the saturation of calcite, dolomite, gypsum, geothite, and hematite mineral due their positive SI values. The principal component analysis (PCA) results possess a total variability of 80.69% signifying the anthropogenic and geogenic source of contamination. The results of the exposure-health-risk-assessment method for measuring As reveal significant potential non-carcinogenic risk (HQ), exceeding the threshold level of (> 1) for children in the study area. Water quality assessment results shows that 24 samples were not suitable for drinking purposes.

Biomonitoring of mercury in water, sediments, and fish (brown and rainbow trout) from remote alpine lakes located in the Himalayas, Pakistan.

Mercury (Hg) contamination of aquatic ecological units and subsequent bioaccumulation are major environmental problems of international scope. Moreover, the biogeochemistry of Hg in the remote alpine lakes aquatic ecosystem in the Himalayas remains largely unexplored. The current study investigated Hg concentrations in different environmental compartments such as water, fish, and sediments in the remote alpine lakes (RALs) including Glacial-fed Lake, Ice melting-fed Lake, and Rain-fed Lake in northern areas of Pakistan. The mean concentration of Hg in Rain-fed Lake water was (1.07 µg L-1), Ice melting-fed Lake (1.16 µg L-1), and Glacial-fed Lake (1.95 µg L-1). For fish muscle tissues, mean concentration of Hg was 1.02 mg kg-1 in the Rain-fed Lake, and 1.2 mg kg-1 for the Ice melting-fed Lake, and 1.51 mg kg-1 in the Glacial-fed Lake. Meanwhile, 0.27 mg kg-1 was observed for sediments in the Rain-fed Lake, 0.33 mg kg-1 for the Ice melting-fed Lake, and 0.38 mg kg-1 for the Glacial-fed Lake, respectively. Chronic daily intake (CDI) and potential health quotient (PHQ) for water showed high health risk in Glacial-fed Lake and low in Rain-fed Lake (PHQ < 1). The target hazard quotient (THQ) values for both the Brown and Rainbow trout in all the studied lakes water were less than 1, indicating no health risk. Furthermore, the Hg level showed high level of contamination in the sediments of all the studied lakes (190 ≤ RI < 380). Overall, Glacial-fed Lake water was more polluted with Hg, as compared to Rain-fed Lake and Ice melting-fed Lake. In the light of the abovementioned results, further research work is urgently needed to shed light on the biological and geochemical monitoring of Hg in arid high-altitude ecosystems along with source identification, mercury speciation, and other potential pollutants.

Multi-geostatistical analyses of the spatial distribution and source apportionment of potentially toxic elements in urban children's park soils in Pakistan: A risk assessment study.

In the past few decades, contamination of urban children's parks (UCPs) with potentially toxic elements (PTEs) has been attracting more and more interest; however, assessment of eco-environmental and child exposure risks particularly in developing countries remains limited. The current study investigated PTE (Cr, Ni, Zn, As, Cd, and Pb) concentrations, potential sources, and their health risk assessment in UCP soils of 12 major cities in Pakistan. The results showed that the mean concentration of Ni exceeded the SEPA-permissible limit in all UCP sites, while other PTEs were found to be within acceptable limits. The soil properties such as pH, electrical conductivity, organic matter, and soil particles size were determined in UCPs soils. The contamination factor and pollution load index results indicated low to moderate pollution levels (CF < 3) and (PLI<1) for all PTEs except Ni in some of the selected cities. Quantile-quantile (Q-Q) plotting determined the normal distribution line for all PTEs in the UCPs. Principal component analysis showed the mixed sources of contamination from industrial emissions, fossil fuel combustion, vehicular emissions, wastewater irrigation, as well as solid waste disposal and natural sources of soil parent materials in all park sites. ANOVA results showed that all the PTEs except Cd had moderate to higher contamination values than the reference site. The risk assessment study revealed that children had high exposure to the selected PTEs via all exposure pathways. The hazard index (HI) mean value (1.82E+00) of Ni for all exposure pathways was greater than 1, while total risk value of Cr (1.00E-03) had exceeded USEPA limit, indicating cancer risk. Consequently, the study of UCPs soils revealed PTEs contamination that could pose a potential health risk to the local population in the studied UCPs regions of Pakistan. Thus, the present study recommends that the influx of PTEs originating from natural and anthropogenic sources should be mitigated and government should implement strict enforcement of environmental regulations and proper management, as well as air quality monitoring guidelines for public health should be strictly adopted to reduce traffic- and industrial emission-related to PTEs in metropolitan areas.

Chemical compounds of the foraging recruitment pheromone in bumblebees.

When the frenzied and irregular food-recruitment dances of bumblebees were first discovered, it was thought that they might represent an evolutionary prototype to the honeybee waggle dance. It later emerged that the primary function of the bumblebee dance was the distribution of an alerting pheromone. Here, we identify the chemical compounds of the bumblebee recruitment pheromone and their behaviour effects. The presence of two monoterpenes and one sesquiterpene (eucalyptol, ocimene and farnesol) in the nest airspace and in the tergal glands increases strongly during foraging. Of these, eucalyptol has the strongest recruitment effect when a bee nest is experimentally exposed to it. Since honeybees use terpenes for marking food sources rather than recruiting foragers inside the nest, this suggests independent evolutionary roots of food recruitment in these two groups of bees.