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.

Assessment of the immobilization effectiveness of several amendments on a cadmium-contaminated soil using Eisenia fetida.

Proper protocols for assessing the remediation effectiveness of contaminated soils are an important part of remediation projects. In the present study, the residual immobilization effectiveness of hydrated lime (L), hydroxyapatite (H), biochar (B) and organic fertilizer (F) alone and in combination was assessed by Eisenia fetida. The results showed that the application of amendments had no significant effect on the death rate and average fresh weight loss of earthworms. The earthworm Cd concentration increased with prolonged exposure time, however, the significant immobilization efficacy of amendments observed on the 7th day nearly disappeared after 28 days of exposure. The immobilization efficiencies, estimated by the earthworms internal Cd concentration, of L, H and B on the 7th day were 38.6%, 37.8% and 20.7%, respectively. These values decreased to 4.9%, 19.8% and 15.1%, respectively, on the 28th day. The detoxification effect of amendments was confirmed by the Cd subcellular fractionation in earthworms with lower proportions of Cd distributed in the metal-sensitive fractions in L, H and B treatments. The level of oxidative stress response of earthworms increased with exposure duration and amendments alleviated the oxidative damage induced by Cd to the earthworms. In addition, the pH and CaCl2-Cd in soils were both increased due to earthworm life activities and gut-related ingestion. In summary, the assessment of immobilization effectiveness of heavy metal-contaminated soils using Eisenia fetida was time-dependent. The immobilization efficacy of L and H performed better than B and F on the 7th day, while H and B performed better than L and F on the 28th day. Accordingly, the short-term earthworm exposure experiment (7 days) was recommended to be an alternative approach to time-consuming plant bioassays in assessment of reduced phytoavailability in chemical immobilization remediation. But the impact of earthworms on the immobilization effect of amendments needs to be considered in practical remediation.

Determination and validation of soil thresholds for cadmium based on food quality standard and health risk assessment.

Cadmium (Cd) is an environmental toxicant with high rates of soil-plant transfer. It is essential to establish an accurate soil threshold for the implementation of soil management practices. This study takes root vegetable as an example to derive soil thresholds for Cd based on the food quality standard as well as health risk assessment using species sensitivity distribution (SSD). A soil type-specific bioconcentration factor (BCF, ratio of Cd concentration in plant to that in soil) generated from soil with a proper Cd concentration gradient was calculated and applied in the derivation of soil thresholds instead of a generic BCF value to minimize the uncertainty. The sensitivity variations of twelve root vegetable cultivars for accumulating soil Cd and the empirical soil-plant transfer model were investigated and developed in greenhouse experiments. After normalization, the hazardous concentrations from the fifth percentile of the distribution based on added Cd (HC5add) were calculated from the SSD curves fitted by Burr Type III distribution. The derived soil thresholds were presented as continuous or scenario criteria depending on the combination of soil pH and organic carbon content. The soil thresholds based on food quality standard were on average 0.7-fold of those based on health risk assessment, and were further validated to be reliable using independent data from field survey and published articles. The results suggested that deriving soil thresholds for Cd using SSD method is robust and also applicable to other crops as well as other trace elements that have the potential to cause health risk issues.

Ecotoxicity of benzo[a]pyrene assessed by soil microbial indicators.

The ecotoxicity of benzo[a]pyrene (BaP) to soil microorganisms was evaluated using the following microbial indicators: soil microbial biomass, respiration, nitrification, and Shannon index. Two soil types, udic ferrosols and aquic cambisols, were amended with 0 mg/kg, 1 mg/kg, 10 mg/kg, 100 mg/kg, 500 mg/kg, or 1000 mg/kg BaP; incubated at 25 °C; and tested on days 28, 60, and 180. The Shannon index was extremely insensitive to BaP. Microbial biomass and respiration could not be classified as sensitive indicators because of their relatively high 10% effect concentration (EC10) values. Nitrification was the most sensitive indicator in both soils and could be the preferred microbial indicator for testing the ecotoxicity of BaP. Higher toxicity of BaP was exhibited in udic ferrosols than in aquic cambisols, and the ecotoxicity of BaP decreased with incubation time. Extending the 28-d incubation time, which is suggested in the International Organization for Standardization and Organisation for Economic Co-operation and Development guidelines, to 60 d was recommended for future microbial toxicity tests of BaP. On day 28, the EC10 values for microbial biomass, respiration, and nitrification were 71 mg/kg, 43 mg/kg, and 3.4 mg/kg in aquic cambisols and 51 mg/kg, 22 mg/kg, and 1.3 mg/kg in udic ferrosols, respectively. On day 60, these values were 106 mg/kg, 59 mg/kg, and 19 mg/kg in aquic cambisols and 77 mg/kg, 40 mg/kg, and 6.9 mg/kg in udic ferrosols. These values could be used in combination to derive ecotoxicological soil screening levels of BaP.