Jingzi Beiyuan

Selective dissolution followed by EDDS washing of an e-waste contaminated soil: Extraction efficiency, fate of residual metals, and impact on soil environment.

To enhance extraction of strongly bound metals from oxide minerals and organic matter, this study examined the sequential use of reductants, oxidants, alkaline solvents and organic acids followed by a biodegradable chelating agent (EDDS, [S,S]-ethylene-diamine-disuccinic-acid) in a two-stage soil washing. The soil was contaminated by Cu, Zn, and Pb at an e-waste recycling site in Qingyuan city, China. In addition to extraction efficiency, this study also examined the fate of residual metals (e.g., leachability, bioaccessibility, and distribution) and the soil quality parameters (i.e., cytotoxicity, enzyme activities, and available nutrients). The reductants (dithionite-citrate-bicarbonate and hydroxylamine hydrochloride) effectively extracted metals by mineral dissolution, but elevated the leachability and bioaccessibility of metals due to the transformation from Fe/Mn oxides to labile fractions. Subsequent EDDS washing was found necessary to mitigate the residual risks. In comparison, prior washing by oxidants (persulphate, hypochlorite, and hydrogen peroxide) was marginally useful because of limited amount of soil organic matter. Prior washing by alkaline solvents (sodium hydroxide and sodium bicarbonate) was also ineffective due to metal precipitation. In contrast, prior washing by low-molecular-weight organic acids (citrate and oxalate) improved the extraction efficiency. Compared to hydroxylamine hydrochloride, citrate and oxalate induced lower cytotoxicity (Microtox) and allowed higher enzyme activities (dehydrogenase, acid phosphatase, and urease) and soil nutrients (available nitrogen and phosphorus), which would facilitate reuse of the treated soil. Therefore, while sequential washing proved to enhance extraction efficacy, the selection of chemical agents besides EDDS should also include the consideration of effects on metal leachability/bioaccessibility and soil quality.

Fate of arsenic before and after chemical-enhanced washing of an arsenic-containing soil in Hong Kong

This study evaluated the feasibility of 2-h chemical-enhanced washing of As-containing soil resulting from geogenic sources in Hong Kong and the fate of As before and after remediation. The soil morphology and As speciation in soil was elucidated by scanning electron microscopy with energy dispersive X-ray spectroscopy, X-ray diffractometer, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Integrated analysis of the results suggests that the As (>90%) resides predominantly as arsenate bound to ferric iron oxides, with a minor contribution (<10%) from an AsIII-sulphide phase. This accounts for the marginal leachability, mobility, and bioaccessibility of geogenic As in the untreated soil despite its high concentration. Among the five types of reagents (organic ligands, reductants, alkaline solvents, inorganic acids, and chelants), only dithionite-citrate-bicarbonate method and alkaline solvents (NaOH and Na2CO3) extracted 37-78% and 26-42% of the As by mineral dissolution. However, these extraction methods notably increased the leachability, mobility, and bioaccessibility of remaining As after soil washing, suggesting that a significant proportion of newly released As is prone to re-adsorption onto the soil surface and becomes highly mobile and bioaccessible. While inorganic acids and chelating agents had marginal effects on the fate of remaining As, organic ligands (citrate, oxalate, or pyrophosphate) probably destabilized the bonding of geogenic As and increased its mobility/bioaccessibility despite marginal extraction. The applicability of chemical extraction of geogenic As is questionable regardless of chemical agents, thus proper management of the As-containing soil by containment or physical encapsulation may be considered before land development.

Chelant-enhanced washing of CCA-contaminated soil: Coupled with selective dissolution or soil stabilization

Remediation of CCA-contaminated soil (Cr, Cu, and As) by biodegradable chelant-enhanced washing (EDDS, S,S-ethylene-diamine-disuccinic-acid) needs further enhancement. This study investigated the effectiveness of coupling with pre-treatment by selective dissolution and post-treatment by soil amendments, respectively. Three groups of reagents (reductants, alkaline solvents, and organic ligands) were adopted in the pre-treatment to dissolve the oxide minerals before EDDS extraction. In the post-treatment, soil amendments (coal fly ash (CFA), acid mine drainage sludge (AMDS), green waste compost (GWC)), and their mixtures) were used for a 2-month stabilization after 2-h EDDS washing. Multi-endpoint evaluation was performed by assessing the chemical state, leachability, mobility, bioaccessibility, and plant-availability of residual metal(loid)s as well as the cytotoxicity, enzyme activities, and available nutrients of the treated soils. Pre-treatment by dithionite-citrate-bicarbonate significantly enhanced extraction efficiency, but also increased the leachability of As and Cr and bioaccessibility of Cr in the treated soils. While sodium hydroxide removed the majority of As without increasing its leachability and bioaccessibility, it increased the cytotoxicity and inhibited the acid phosphatase activity. Post-treatment with AMDS and CFA effectively controlled the mobility and leachability of residual As and Cr after EDDS washing. However, destabilized Cu was only marginally immobilized by GWC due to strong Cu-EDDS complexation. The bioaccessibility and phytoavailability of Cu was primarily reduced by EDDS washing, while those of As and Cr could be attenuated by AMDS and CFA. This study indicates that coupling chemical extraction with subsequent soil amendment plays complementary roles in mitigating effects of residual metal(loid)s and improving environmental quality.

A combination of ferric nitrate/EDDS-enhanced washing and sludge-derived biochar stabilization of metal-contaminated soils

In this study, soil washing and stabilization as a two-step soil remediation strategy was performed to remediate Pb- and Cu-contaminated soils from shooting range and railway sites. Ferric nitrate (Fe(NO3)3) and [S,S]-ethylenediamine disuccinate (EDDS) were used as washing agents, whereas three types of sludge-derived biochars and phosphogypsum were employed as soil stabilizers. While Fe(NO3)3 extracted larger amounts of metals compared to EDDS (84% Pb and 64% Cu from shooting range soil; 30% Pb and 40% Cu from railway site soil), it caused severe soil acidification. Both Fe(NO3)3 and EDDS washing enhanced the mobility of residual metals in the two soils, which in most cases could be mitigated by subsequent 2-month stabilization by sludge-derived biochars or phosphogypsum. By contrast, the metal bioaccessibility could only be reduced by soil washing. Nutrient-rich sludge-derived biochar replenished available P and K in both soils, whereas Fe(NO3)3 washing provided available nitrogen (N). Soil amendment enhanced acid phosphatase activity but marginally improved soil dehydrogenase and urease activity in the treated soils, possibly due to the influence of residual metals. This study supported the integration of soil washing (by Fe(NO3)3 or EDDS) with soil stabilization (by sludge-derived biochars or phosphogypsum) for accomplishing the reduction of metal mobility and bioaccessibility, while restoring the environmental quality of the treated soils.

Pine sawdust biomass and biochars at different pyrolysis temperatures change soil redox processes

To date, no investigation has been carried out to explore the effects of biochars produced at different pyrolysis temperatures on the dynamics of redox potential (EH) and pH in a contaminated floodplain soil. Thus, we aimed to quantify the dynamics of EH and pH in contaminated flooded soils treated with 70tha-1 of pine sawdust biomass (S&BM) and biochars pyrolyzed at 300°C (S&BC300) and 550°C (S&BC550) and pre-incubated for 105days in an automated biogeochemical microcosm system. Microbial community composition was also determined via analyzing phospholipid fatty acid (PLFA).We found that BC300 and BC550 treatments substantially decreased (3-6.5%) and BM increased (~37%) the mean of soil EH compared to the untreated contaminated soil (CS).·The largest EH decline in S&BC550 was at the rate of -80mVh-1 at 10h while it was observed at 25h in S&BC300 and 20-25h in S&BM or CS, respectively. At high EH, a higher total PLFA biomass and microbial groups in the CS (71-87%) were found in comparison to treated soils. Higher aromaticity and ash content in BC550 than BC300 and BM led to the greater PLFA biomass and microbial groups which contributed to higher capacity of accepting and donating electrons in soil slurry and were probably one reason for the largest decrease in EH. Pine sawdust biomass and BCs have a noticeable influence in soil biogeochemical processes relevant to fluctuating redox conditions.

Dynamic leaching behavior of geogenic As in soils after cement-based stabilization/solidification

Cement-based stabilization/solidification (S/S) is a practical treatment approach for hazardous waste with anthropogenic As sources; however, its applicability for geogenic As-containing soil and the long-term leaching potential remain uncertain. In this study, semi-dynamic leaching test was performed to investigate the influence of S/S binders (cement blended with fuel ash (FA), furnace bottom ash (FBA), or ground granulated blast furnace slag (GGBS)) on the long-term leaching characteristics of geogenic As. The results showed that mineral admixtures with higher Ca content and pozzolanic activity were more effective in reducing the leached As concentrations. Thus, cement blended with FBA was inferior to other binders in suppressing the As leaching, while 20% replacement of ordinary Portland cement by GGBS was considered most feasible for the S/S treatment of As-containing soils. The leachability of geogenic As was suppressed by the encapsulation effect of solidified matrix and interlocking network of hydration products that were supported by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) results. The long-term leaching of geogenic As from the monolithic samples was diffusion-controlled. Increasing the Ca content in the samples led to a decrease in diffusion coefficient and an increase in feasibility for “controlled utilization” of the S/S-treated soils.

Effects of low-alkalinity binders on stabilization/solidification of geogenic As-containing soils: Spectroscopic investigation and leaching tests.

The low-alkalinity stabilization/solidification (S/S) treatment of the soil containing high concentrations of geogenic As by physical encapsulation is considered as a proper management before land development; however, the choice of an effective binder and the leaching potential of As remain uncertain. In this study, the influence of S/S binders (cement blended with fuel ash (FA), furnace bottom ash (FBA), or ground granulated blast furnace slag (GGBS)) on the speciation and leaching characteristics of geogenic As was studied. The results of X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS) showed the reduced amount of calcium silicate hydrate phase and the decrease in oxidation state of As(V)-O on the surface of Fe(III) oxides/hydroxides in the low-alkalinity S/S treated soils. This might be due to the binder incorporation and change in pH conditions, which slightly affected the As-Fe interaction and increased the non-specifically sorbed species of As. Therefore, the S/S treatment increased the leachability and bioaccessibility of geogenic As to varying degree but decreased the phyto-extractable As. The S/S treatment by cement incorporating 25% of class C fly ash (O4C1) could achieve comparable or better performance, while reducing the risk assessment code (RAC) to a greater extent compared to that of using cement only. This study illustrates the effectiveness and limitations of low-alkalinity binders (e.g., O4C1) for geogenic As immobilization and encapsulation, which provides a new insight for determining the appropriate S/S binder in soil remediation.

Combined application of EDDS and EDTA for removal of potentially toxic elements under multiple soil washing schemes

Chelant-enhanced soil washing, such as EDTA (ethylenediaminetetraacetic acid) and biodegradable EDDS ([S,S]-ethylene-diamine-disuccinic acid), has been widely studied, however, EDTA is persistent under natural conditions while EDDS has a low efficiency for Pb extraction. Therefore, we investigated the efficacy of mixed chelants (EDDS and EDTA mixture at 1:1 M ratio) for the removal of Cu, Zn, and Pb from a field-contaminated soil using various washing schemes (multi-pulse, step-gradient chelant, and continuous washing schemes). Speciation modelling of the target metals, mineral elements, and EDDS/EDTA was performed, while the leachability and bioaccessibility of residual metals in the treated soils were also assessed. Our results suggested that the combined use of EDDS and EDTA reached equivalent extraction efficiency of the target metals as EDTA, i.e., 50% reduction in the dosage of EDTA was made possible. This was accomplished by selective extraction of Cu by EDDS and Pb by EDTA, which was supported by the results of speciation calculation. Multi-pulse washing scheme with intermittent water rinsing steps removed entrapped metal-chelant complexes and free chelants, therefore reducing the leachability and bioaccessibility of residual metals in the treated soils. Step-gradient chelant washing with the maximum dosage of chelants in the first washing step only achieved marginal improvement but undesirably promoted Pb bioaccessibility. Continuous washing for 24 h enhanced metal extraction but promoted mineral dissolution, together with a large amount of uncomplexed chelants and increase in Cu leachability. Thus the combined use of EDDS and EDTA in multi-pulse washing is recommended for further studies.