Zhengtao Shen

Long-term impact of biochar on the immobilisation of nickel (II) and zinc (II) and the revegetation of a contaminated site

A field remediation treatment was carried out to examine the long-term effect of biochar on the immobilisation of metals and the revegetation of a contaminated site in Castleford, UK. The extracted concentrations of nickel (Ni) (II) and zinc (Zn) (II) in the carbonic acid leaching tests were reduced by 83-98% over three years. The extracted Ni (II) and Zn (II) concentrations three years after the treatment were comparable to a cement-based treatment study carried out in a parallel manner on the same site. The sequential extraction results indicated that biochar addition (0.5-2%) increased the residue fractions of Ni (II) (from 51% to 61-66%) and Zn (II) (from 7% to 27-35%) in the soils through competitive sorption, which may have resulted in the reduction of leachabilities of Ni (II) (from 0.35% to 0.12-0.15%) and Zn (II) (from 0.12% to 0.01%) in the plots with biochar compared with that without biochar three years after the treatment. The germination of grass in the plots on site failed. Further laboratory pot study suggested that larger amounts of biochar (5% or more) and compost (5% or more) were needed for the success of revegetation on this site. This study suggests the effectiveness and potential of biochar application in immobilising heavy metals in contaminated site in the long term.

Sorption of lead by Salisbury biochar produced from British broadleaf hardwood

In this study, the physicochemical properties of Salisbury biochar produced from British broadleaf hardwood and its adsorption characteristics towards lead were investigated. The biochar particle size has a significant effect on its BET surface area, cation exchange capacity and sorption of lead. The kinetics data were well fitted by the Pseudo second order model. The increase of biochar dosage increased the percentage of lead removal in solutions. The increase of initial solution pH increased the percentage of lead removal across the pH range of 2-10. The calculated maximum adsorption capacities of lead by Langmuir model were 47.66 and 30.04 mg/g for 0.15 mm and 2 mm samples. The adsorption capacities of different metals decreased in the order of lead > nickel > copper > zinc calculated in mmol/g. This study suggests a great potential of biochars derived from British broadleaf hardwood to be applied in soil remediation.

Biochar application for the remediation of heavy metal polluted land: A review of in situ field trials

Polluted land is a global issue, especially for developing countries. It has been reported that soil amendment with biochar may reduce the bioavailability of a wide range of contaminants, including heavy metal(loids), potentially reclaiming contaminated soils for agricultural use. However, there have been only limited reports on the in situ application of biochar at the field scale. This review was devoted to providing preliminary scientific evidence from these field trials, based on a review of 29 publications involving field applications of biochar in 8 different countries. The data show that biochars effectiveness in reducing the impacts of pollution depends on a myriad of factors in the field, including the application time period, site-specific factors (e.g. climate, biochar dosage rate, and mixing depth), biochar feedstock type, and biochar properties. The results of this review indicate that biochar application can potentially reduce contaminant bioavailability in the field; for instance, a significant decrease (control normalized mean value=0.55) in the Cd enrichment of rice crops was observed. It was found that the use of biochar may help increase crop yields on polluted land, and thus reduce the amount of mineral fertilizer used in the field. However, in order to maximize the benefits of biochar addition, farmers need to accept that the dosage rates of mineral fertilizers should be reduced. This review also revealed that the effectiveness of biochar in mitigating pollution may decrease with time due to ageing factors, such as leaching of biochar alkalinity.

Qualitative and quantitative characterisation of adsorption mechanisms of lead on four biochars

The adsorption mechanisms of lead (Pb2+) on four biochars (SB produced from British hardwood at 600°C and three standard biochars produced from wheat straw pellets at 700°C (WSP700), rice husk at 700°C (RH700) and soft wood pellets at 550°C (SWP550)) were characterised qualitatively and quantitatively, using a combination of chemical and micro-structural methods. Sequential extraction test results show that Pb2+ was predominantly adsorbed on SB (85.31%), WSP700 (75.61%) and RH700 (85.76%) as acidic soluble fraction, which was potentially bioavailable if applied in soil. The exchangeable fraction for SB, WSP700 and RH700 was low (1.38-4.29%) and their water soluble fraction was negligible (0-0.14%). Micro-structural analysis further investigated this fraction and confirmed the presence of cerussite (PbCO3) on SB and hydrocerussite (Pb3(CO3)2(OH)2) on WSP700, RH 700 and SWP550, suggesting a mechanism of surface precipitation for Pb2+ adsorption on the biochars. The percentages of Pb2+ in the form of PbCO3 on SB (82.24%) and Pb3(CO3)2(OH)2 on WSP700 (13.00%), RH 700 (19.19%) and SWP550 (29.70%) were quantified using thermogravimetric analysis (TGA). This study suggests that it is feasible to quantify different adsorption mechanisms of Pb2+ on biochars, which is important for the practical application of biochar in water and/or soil treatment.

Salisbury biochar did not affect the mobility or speciation of lead in kaolin in a short-term laboratory study

Salisbury biochar (produced from British broadleaf hardwood) with two different particle sizes (≤2mm and ≤0.15mm) was applied on a kaolin with three different lead (Pb(2+)) contamination levels (50mg/kg, 300mg/kg and 1000mg/kg) at the dosage of 1% in w/w. The short-term impact of biochar on the mobility and speciation of Pb(2+) in the kaolin was investigated using attenuation periods of 1, 7 and 28 days. The leachability and extractability of Pb(2+) in carbonic acid leaching and EDTA extraction tests as well as the speciation of Pb(2+) in soils were not significantly affected by biochar treatment during all periods. The insignificant effects of biochar on Pb(2+) immobilisation were most likely attributed to the high adsorption capacity of Pb(2+) on the kaolin and biochar failed to competitively adsorb Pb(2+) against kaolin. The kaolin immobilised Pb(2+) primarily through cation exchange, which represents the readily bioavailable fractions of Pb(2+) in soils and may still pose environmental risks. This paper suggests the inefficiency of biochar treament on heavy-metal contaminated clay-rich soils. Therefore a laboratory treatablity study with respect to the soil type may be crucial when large-scale biochar applications in heavy-metal associated soil remediation are evaluated.

Stability of heavy metals in soil washing residue with and without biochar addition under accelerated ageing

Soil washing residue (SWR), which typically concentrates the washed toxic metals and is comprised of high contents of clay particles, may pose risks to the surrounding environment. This study aims to simulate accelerated ageing to assess the stability of selected metals (Cd2+ (132mg/kg), Cu2+ (248mg/kg) and Pb2+ (3470mg/kg)) in a SWR (89.68% of clay) with and without biochar treatment. The soil was incubated under constant moisture and wet-dry cycles (accelerated ageing), respectively, and the mobility and fractions of heavy metals in the soils with and without biochar treatment were examined. Under the constant moisture condition, biochar addition at 5% w/w reduced the leached Cd2+ (by 1.81%) and Cu2+ (by 8.70%) from SWR at day 1 and the leached Cu2+ (by 51.08%) and Pb2+ (by 25.36%) from SWR at day 14; however, the leached metals in the TCLP solution from the biochar-amended soils still exceed the regulatory limits (1mg/L for Cd2+, 5mg/L for Pb2+, no regulatory limits for Cu2+). Conversely, accelerated ageing (14days) significantly increased the fractions of exchangeable Cd2+ (from 3.63-3.94% to 6.21-6.29%) and Pb2+ (from 0.025-0.027% to 0.034-0.041%) as well as the TCLP leachabilities of Cd2+ (from 2.91-3.28% to 3.46-3.73%), Cu2+ (from 0.08-0.10% to 0.03-0.06%) and Pb2+ (from 0.25-0.35% to 0.52-0.57%) in the soils, as compared with those incubated under constant moisture, regardless of biochar addition. This study reveals challenges associated with stabilising SWR due to the presence of residual fine-grained particles.

Assessing long-term stability of cadmium and lead in a soil washing residue amended with MgO-based binders using quantitative accelerated ageing

A soil washing residue (SWR) (containing 90% clay, cadmium (Cd2+) of 132 mg/kg, lead (Pb2+) of 3410 mg/kg) was stabilized with MgO (M) and MgO + bioapatite (MB) respectively at a dosage of 5% in w/w. The stability of the metals in original and amended SWRs was assessed after immediate treatment and using a laboratory accelerated ageing method simulating 26, 52, 78 and 104 years in field conditions. The dissolved Cd2+ and Pb2+ from the SWR in Toxicity Characteristic Leaching Procedure (TCLP) leachates significantly reduced (by 96.84-99.06%) by both amendments after immediate treatment. The stabilization remained effective within simulated 26 years as the TCLP leached Cd2+ and Pb2+ kept below regulatory levels. This immobilization was mainly due to the increased non-bioavailable Cd2+ and Pb2+ from sequential extraction tests in SWR by the amendments. At simulated 52 years, the TCLP leached Cd2+ from M and MB exceeded regulatory level by 106% and 1% respectively. Large amounts of Cd2+ and Pb2+ were leached out by 36.74-48.18% regardless of the treatments at simulated 104 years. Although bioapatite can significantly aid the stabilization of metals by MgO, the stabilization effectiveness for both treatments diminished at simulated 52 years and from 52 to 104 years.

Kinetic and equilibrium modelling of MTBE (Methyl tert-butyl ether) adsorption on ZSM-5 zeolite: batch and column studies

The intensive use of methyl tert-butyl ether (MTBE) as a gasoline additive has resulted in serious environmental problems due to its high solubility, volatility and recalcitrance. The feasibility of permeable reactive barriers (PRBs) with ZSM-5 type zeolite as a reactive medium was explored for MTBE contaminated groundwater remediation. Batch adsorption studies showed that the MTBE adsorption onto ZSM-5 follows the Langmuir model and obeys the pseudo-second-order model with an adsorption capacity of 53.55 mg g-1. The adsorption process reached equilibrium within 24 h, and MTBE was barely desorbed with initial MTBE concentration of 300 mg L-1. The mass transfer process is found to be primarily controlled by pore diffusion for MTBE concentrations from 100 to 600 mg L-1. pH has little effect on the maximum adsorption capacity in the pH range of 2-10, while the presence of nickel reduces the capacity with Ni concentrations of 2.5-25 mg L-1. In fixed-bed column tests, the Dose-Response model fits the breakthrough curve well, showing a saturation time of ∼320 min and a removal capacity of ∼18.71 mg g-1 under the conditions of this study. Therefore, ZSM-5 is an extremely effective adsorbent for MTBE removal and has a huge potential to be used as a reactive medium in PRBs.

Lead-based paint in children's toys sold on China's major online shopping platforms

Lead in paint is a major public health concern and has drawn much attention from international organizations such as the World Health Organization (WHO) and the United Nations Environmental Programme (UNEP). However, there is limited research on lead-based paint, especially its use in toys, which poses an explicit health risk to vulnerable children. The present study sampled 100 different toys purchased from the three largest online shopping platforms in China: JD, Taobao (TB) and Tmall (TM). These selected toys have been sold nearly 3 million times in total, suggesting that they may have reached the dwellings of millions of children. It was found that the toys sold by JD and TM, which are considered organized sellers, had average lead concentrations of 25 mg/kg and 32 mg/kg, respectively, much lower than that of toys sold by unorganized sellers on the TB platform, at 219 mg/kg. Approximately 12% of the toys purchased from TB contained paint with total lead concentrations exceeding Chinas regulatory standard for paints in toy manufacturing, and nearly 36% of the toys purchased from TB exceeded the equivalent US regulatory standard and EU standard. These results suggest that further action is needed to verify the health and safety standards of toys sold by such unorganized sellers. Moreover, this study found that Chinas regulatory standard (90 mg/kg) based on soluble lead may underestimate the risk posed by lead in paints, and it is suggested that future regulatory thresholds for lead levels in paints for toy manufacture be based on total rather than soluble lead concentrations. The present study also explored various influencing factors on lead concentration, and found that lead concentrations were related to toy price, age group, color, and sales volume.

Breakthrough Curve Modelling of ZSM-5 Zeolite Packed Fixed-Bed Columns for the Removal of MTBE

ZSM-5, as a hydrophobic zeolite, has a good adsorption capacity for MTBE in batch adsorption studies. This study explores the potential of ZSM-5 as an adsorbent for MTBE in a laboratory scale fixed-bed column study. A series of column tests were carried out to determine the breakthrough curves and evaluate the adsorption performance at different bed lengths. Logit method, Adams-Bohart model, Yoon and Nelson model and Dose-Response model were applied to fit the experimental data in order to predict the breakthrough curves and determine the adsorption kinetics of MTBE onto ZSM-5 in the fixed-bed columns. Dose-Response model was found to best describe the breakthrough curves and the maximum adsorption capacity increased with the increase of bed length. In addition, ZSM-5 can be thermally regenerated at 80 °C and the MTBE removal percentage still remained at >85% after 4 regeneration cycles.