Faecal and nitrate contamination in the groundwater of Mardan district, Pakistan.

This study aimed to determine the status of groundwater contamination with faecal coliform and nitrate in the rural areas of Mardan district, Pakistan. Both analytes require regular monitoring according to the National Environmental Quality Standards (NEQS) of Pakistan. Groundwater samples (n = 100) were collected from 25 villages across four zones. Samples were analysed for physicochemical parameters including pH, electrical conductivity (EC), Escherichia coli (E. coli) contamination, nitrite, and nitrate ([Formula: see text] and [Formula: see text]). Whilst the average concentrations of [Formula: see text] in the water samples were within the permissible limits of 50 mg L-1 set by the World Health Organisation (WHO) and NEQS two villages exceeded the safety limits. Non-carcinogenic health risks of [Formula: see text] were estimated in terms of average daily dose (ADD) and hazard quotient (HQ). The HQ values for [Formula: see text] were > 1 for children signifying potential health risks; however, the adult population had HQ < 1 which indicates no risk. Groundwater samples tested positive for E. coli contamination in 13 villages, suggesting that residents may be living at risk of various microbial diseases due to drinking of contaminated water. The findings of this study provide valuable baseline data for groundwater researchers, policymakers, and the local public health department.

Biochar efficacy for reducing heavy metals uptake by Cilantro (Coriandrum sativum) and spinach (Spinaccia oleracea) to minimize human health risk.

Environmentally friendly and cost-effective techniques are required to reclaim land degraded during mining activities. Bioaccumulation of heavy metals (HMs) in vegetables grown on contaminated soils can increase human health risks. The potential effects of hardwood biochar (HWB) was assessed for chromium (Cr), zinc (Zn), copper (Cu), manganese (Mn) and lead (Pb) bioavailability in mine-contaminated soils and their subsequently bioaccumulation in crops and associated health risk. HWB was applied to chromium-manganese mine contaminated soils at the rate of 3% to investigate the efficiency of HWB for the second crop in crop rotation technique. Cilantro (Coriandrum sativum) and spinach (Spinaccia oleracea) were grown as second crop in the same pots which were already used for rice cultivation as first crop (without adding further amendments). Application of HWB decreased the concentrations of Cr, Zn, Cu, Mn, and Pb in cilantro by 25.5%, 37.1%, 42.5%, 34.3%, and 36.2%, respectively as compared to control. In spinach, the reduction in concentrations of Cr was 75.0%, Zn 24.1%, Cu 70.1%, Mn 78.0%, and Pb 50.5% as compared to control. HWB significantly (P < 0.01) reduced the HMs uptake in spinach cultivated in the amended soils as compared to the spinach in control. Bioaccumulation factor results also indicate that HWB decreased the bioaccumulation of selected HMs in cilantro and spinach, thus reducing health risks. Results of the study clearly demonstrate that the use of HWB can significantly reduce HMs in vegetables, associated health risk and improve food quality, therefore can be used as soil amendment for reclamation of mine-degraded soils.

Sorption of ammonium and nitrate to biochars is electrostatic and pH-dependent.

Biochars are potentially effective sorbents for NH4+ and NO3- in water treatment and soil applications. Here we compare NH4+ and NO3- sorption rates to acid-washed biochars produced from red oak (Quercus rubra) and corn stover (Zea mays) at three pyrolysis temperatures (400, 500 and 600 °C) and a range of solution pHs (3.5-7.5). Additionally, we examined sorption mechanisms by quantification of NH4+ and NO3- sorption, as well as Ca2+ and Cl- displacement for corn stover biochars. Solution pH curves showed that NH4+ sorption was maximized (0.7-0.8 mg N g-1) with low pyrolysis temperature (400 °C) biochar at near neutral pH (7.0-7.5), whereas NO3- sorption was maximized (1.4-1.5 mg N g-1) with high pyrolysis temperatures (600 °C) and low pH (3.5-4). The Langmuir (r2 = 0.90-1.00) and Freundlich (r2 = 0.81-0.97) models were good predictors for both NH4+ (pH 7) and NO3- (pH 3.7) sorption isotherms. Lastly, NH4+ and NO3- displaced Ca2+ and Cl-, respectively, from previously CaCl2-saturated corn stover biochars. Results from the pH curves, Langmuir isotherms, and cation displacement curves all support the predominance of ion exchange mechanisms. Our results demonstrate the importance of solution pH and chemical composition in influencing NH4+ and NO3- sorption capacities of biochar.

Impact of Biochar Organic and Inorganic Carbon on Soil CO2 and N2O Emissions.

Biochar has been shown to influence soil CO and NO emissions following application to soil, but the presence of carbonates in biochars has largely confounded efforts to differentiate among labile and recalcitrant C pools in biochar and establish their timeframe of influence. Understanding the mechanism, magnitude, and duration of biochar C pools' influence on C and N dynamics is imperative to successful implementation of biochar for C sequestration. Here we therefore aim to assess biochar organic and inorganic C pool impacts on CO and NO emissions from soil amended with two untreated biochars, inorganic carbon (as NaCO), acid (HCl) and bicarbonate (NaHCO) extracts of the biochars, and acid and bicarbonate/acid-washed biochars during a 140-d soil incubation. We hypothesized that (i) both biochar labile organic carbon (LOC) and inorganic carbon (IC) pools contribute significantly to short-term (<1 mo) CO emissions from biochar-amended soil, (ii) biochars will influence the size of soil NH and NO pools, and (iii) changes in soil inorganic N pools will affect soil NO emissions. All biochar, biochar extract, and carbonate treatments (12 total) increased CO produced during the initial ≤48 h of the incubation relative to controls, indicating that both biochar LOC and IC contribute to CO emissions. Of these treatments, only bicarbonate extracts of the biochars increased total C losses significantly. However, treatment impacts on soil NO production were not significant despite significant effects of select treatments on inorganic N pools. Overall, results indicate that biochars contain small LOC and IC pools that are stabilized by a larger recalcitrant organic C pool.

Characterization and quantification of biochar alkalinity.

Lack of knowledge regarding the nature of biochar alkalis has hindered understanding of pH-sensitive biochar-soil interactions. Here we investigate the nature of biochar alkalinity and present a cohesive suite of methods for its quantification. Biochars produced from cellulose, corn stover and wood feedstocks had significant low-pKa organic structural (0.03-0.34 meq g-1), other organic (0-0.92 meq g-1), carbonate (0.02-1.5 meq g-1), and other inorganic (0-0.26 meq g-1) alkalinities. All four categories of biochar alkalinity contributed to total biochar alkalinity and are therefore relevant to pH-sensitive soil processes. Total biochar alkalinity was strongly correlated with base cation concentration, but biochar alkalinity was not a simple function of elemental composition, soluble ash, fixed carbon, or volatile matter content. More research is needed to characterize soluble biochar alkalis other than carbonates and to establish predictive relationships among biochar production parameters and the composition of biochar alkalis.

Evaluation of modified boehm titration methods for use with biochars.

The Boehm titration, originally developed to quantify organic functional groups of carbon blacks and activated carbons in discrete pK ranges, has received growing attention for analyzing biochar. However, properties that distinguish biochar from carbon black and activated carbon, including greater carbon solubility and higher ash content, may render the original Boehm titration method unreliable for use with biochars. Here we use seven biochars and one reference carbon black to evaluate three Boehm titration methods that use (i) acidification followed by sparging (sparge method), (ii) centrifugation after treatment with BaCl (barium method), and (iii) a solid-phase extraction cartridge followed by acidification and sparging (cartridge method) to remove carbonates and dissolved organic compounds (DOC) from the Boehm extracts before titration. Our results for the various combinations of Boehm reactants and methods indicate that no one method was free of bias for all three Boehm reactants and that the cartridge method showed evidence of bias for all pK ranges. By process of elimination, we found that a combination of the sparge method for quantifying functional groups in the lowest pK range (∼5 to 6.4), and the barium method for quantifying functional groups in the higher pK ranges (∼6.4 to 10.3 and ∼10.3 to 13) to be free of evidence for bias. We caution, however, that further testing is needed and that all Boehm titration results for biochars should be considered suspect unless efforts were undertaken to remove ash and prevent interference from DOC.