Iron-modified phosphorus- and silicon-based biochars exhibited various influences on arsenic, cadmium, and lead accumulation in rice and enzyme activities in a paddy soil.

Contamination of paddy soils with potentially toxic elements (PTEs) has become a severe environmental issue. Application of functionalized biochar for rice cultivation has been proposed as an effective means to reduce environmental risks of these PTEs in paddy soils. This work was undertaken to seek the positive effects of a rice husk-derived silicon (Si)-rich biochar (Si-BC) and a pig carcass-derived phosphorus (P)-rich biochar (P-BC), as well as their Fe-modified biochars (Fe-Si-BC and Fe-P-BC) on the enzyme activity and PTE availability in an As-Cd-Pb-contaminated soil. A rice cultivation pot trial was conducted using these functionalized biochars as soil amendments for the alleviation of PTE accumulation in rice plants. Results showed that Si-BC decreased the concentrations of As in rice grain and straw by 59.4 % and 61.4 %, respectively, while Fe-Si-BC significantly (P < 0.05) enhanced plant growth, increasing grain yield (by 38.6 %). Fe-Si-BC significantly (P < 0.05) elevated Cd and Pb accumulation in rice plants. P-BC enhanced the activities of dehydrogenase, catalase, and urease, and reduced grain-Pb and straw-Pb by 49.3 % and 43.2 %, respectively. However, Fe-P-BC reduced plant-As in rice grain and straw by 12.2 % and 51.2 %, respectively, but increased plant-Cd and plant-Pb. Thus, Fe-modified Si- and P-rich biochars could remediate paddy soils contaminated with As, and enhance the yield and quality of rice. Application of pristine P-rich biochar could also be a promising strategy to remediate the Pb-contaminated paddy soils and limit Pb accumulation in rice.

Potentially toxic elements exposure biomonitoring in the elderly around the largest polymetallic rare earth ore mining and smelting area in China.

Potentially toxic elements (PTEs) can be released during mining operations and ore processing. The pollution and health risk related to PTEs in total suspended particulates (TSPs) around the largest polymetallic rare earth mining area (Bayan Obo) and smelting area (Baotou) in Inner Mongolia, China, were evaluated. PTEs in the hair of the elderly living in these two areas and a reference area (Hohhot) were also examined. Relationships between PTEs in TSPs and hair with categorical factors (location, gender, etc.) were also modeled. Multivariate statistical analyses were carried out to analyze the possible sources of the PTEs in TSPs. The bubble maps of the concentrations of PTEs indicated that high concentrations of PTEs were near the industrial area where smelting plants and power plants were located. In addition, health risks were assessed for adults in the mining and smelting area. The carcinogenic risk of Cr was high for residents in the study areas. Also, the residents were exposed to a non-carcinogenic risk of Ni. Significant mean value differences were observed between PTEs in the hair of the elderly in Baotou and Hohhot. Results of the linear regression model indicated that around 31 % of the Pb in hair could be explained by the linear regression model, it could be affected by Ni and Zn in TSPs, but location, gender, and sampling time showed no significant contribution. Age was not significantly associated with the PTEs levels in hair in Baotou and Bayan Obo. The results provide important scientific evidence for a better understanding of the effects of PTEs in TSPs in polymetallic ore mining and smelting areas.

Effect of biochar aging and co-existence of diethyl phthalate on the mono-sorption of cadmium and zinc to biochar-treated soils.

In this study, the influence of the aging process of pig-(PB) and P. orientalis-(POB) derived biochars on the sorption capacity of the biochar-treated soils for cadmium (Cd) and zinc (Zn) with and without the co-existence of diethyl phthalate (DEP) was investigated. Additionally, the surface and internal characteristics of biochars were determined before and after their aging in soils. The PB-treated soil had a higher sorption capacity for Cd2+ and Zn2+ than the POB-treated soil. The sorption capacity of the biochar-treated soils for Cd2+ and Zn2+ increased with biochar application rates. After aging, the abundance of oxygen-containing functional groups on the biochar surface, and the pH and organic carbon content of the biochar-treated soils significantly increased, thereby improving the sorption capacity for Cd2+ and Zn2+. The sorption capacities of biochar-treated soils for Cd2+ and Zn2+ followed the order of 1-month aging > 6-month aging > fresh. The co-existence of DEP enhanced the sorption capacity of the fresh biochar-treated soils for Cd2+ and Zn2+, whereas this enhancing effect disappeared for the aged biochar treatments. Our findings provide insights into the interactions between mixed contaminants in biochar-amended soils and the long-term efficacy of biochar treatments on metal sorption to soils.

Iron-modified biochar and water management regime-induced changes in plant growth, enzyme activities, and phytoavailability of arsenic, cadmium and lead in a paddy soil.

The aim of this study was to evaluate the effect of raw (RawBC) and iron (Fe)-modified biochar (FeBC) derived from Platanus orientalis Linn branches on the plant growth, enzyme activity, and bioavailability and uptake of As, Cd, and Pb by rice in a paddy soil with continuously flooded (CF) or alternately wet and dry (AWD) irrigation in a pot experiment. Application of RawBC (3%, w/w) significantly increased soil pH, while FeBC decreased it. The FeBC was more effective in reducing As and Pb bioavailability, particularly under the AWD water regime, while RawBC was more conducive in reducing Cd bioavailability under the CF water regime. The FeBC decreased As concentration, but increased concentrations of Cd and Pb in the straw and brown rice, as compared to the untreated soil. Soil catalase and urease activities were enhanced by RawBC, but decreased by FeBC treatment. The FeBC increased the grain yield by 60% and 32% in CF and AWD treatments, respectively. The FeBC can be recommended for immobilization of As in paddy soils, but a potential human health risk from Cd and Pb in FeBC-treated soils should be considered due to increased uptake and translocation of the metals to brown rice.

Fabrication of engineered biochar from paper mill sludge and its application into removal of arsenic and cadmium in acidic water.

An engineered biochar was fabricated via paper mill sludge pyrolysis under CO2 atmosphere, and its adsorption capability for As(V) and Cd(II) in aqueous solution was evaluated in a batch mode. The characterization results revealed that the biochar had the structure of complex aggregates containing solid minerals (FeO, Fe3O4 and CaCO3) and graphitic carbon. Adsorption studies were carried out covering various parameters including pH effect, contact time, initial concentrations, competitive ions, and desorption. The adsorption of As(V) and Cd(II) reached apparent equilibrium at 180min, and followed the pseudo-second-order kinetics. The highest equilibrium uptakes of As(V) and Cd(II) were 22.8 and 41.6mgg-1, respectively. The adsorption isotherms were better described by Redlich-Peterson model. The decrease in As(V) adsorption was apparent with the increase in PO43- concentration, and a similar inhibition effect was observed for Cd(II) adsorption with Ni(II) ion. The feasibility of regeneration was demonstrated through desorption by NaOH or HCl.

The role of magnetite nanoparticles in the reduction of nitrate in groundwater by zero-valent iron.

Magnetite nanoparticles were used as an additive material in a zero-valent iron (Fe0) reaction to reduce nitrate in groundwater and its effects on nitrate removal were investigated. The addition of nano-sized magnetite (NMT) to Fe0 reactor markedly increased nitrate reduction, with the rate proportionally increasing with NMT loading. Field emission scanning electron microscopy analysis revealed that NMT aggregates were evenly distributed and attached on the Fe0 surface due to their magnetic properties. The rate enhancement effect of NMT is presumed to arise from its role as a corrosion promoter for Fe0 corrosion as well as an electron mediator that facilitated electron transport from Fe0 to adsorbed nitrate. Nitrate reduction by Fe0 in the presence of NMT proceeded much faster in groundwater (GW) than in de-ionized water. The enhanced reduction of nitrate in GW was attributed to the adsorption or formation of surface complex by the cationic components in GW, i.e., Ca2+ and Mg2+, in the Fe0-H2O interface that promoted electrostatic attraction of nitrate to the reaction sites. Moreover, the addition of NMT imparted superior longevity to Fe0, enabling completion of four nitrate reduction cycles, which otherwise would have been inactivated during the first cycle without an addition of NMT. The results demonstrate the potential applicability of a Fe0/NMT system in the treatment of nitrate-contaminated GW.

The effect of granular ferric hydroxide amendment on the reduction of nitrate in groundwater by zero-valent iron.

The feasibility of using granular ferric hydroxide (GFH) with zero-valent iron (Fe(0)) for its potential utility in enhancing nitrate reduction was investigated. The addition of 10gL(-1) GFH to 25gL(-1) Fe(0) significantly enhanced nitrate removal, resulting in 93% removal of 52.2mg-NL(-1) in 36-h as compared to 23% removal with Fe(0) alone. Surface analyses of the reacted Fe(0)/GFH revealed the presence of magnetite on the Fe(0) surface, which probably served as an electron mediator for nitrate reduction. Addition of GFH to Fe(0) also resulted in lower solution pH compared to Fe(0). The rate enhancing effect of GFH on nitrate reduction was attributed to the combined effects of magnetite formation and pH buffering by GFH. GFH amendment (100gL(-1)) significantly increased reduction capacity and longevity of Fe(0) to complete several nitrate reduction cycles before inactivation, giving a total nitrate removal of 205mg-NL(-1), while unamended Fe(0) gave only 20mg-NL(-1) before inactivation during the first reduction cycle. The overall result demonstrated the potential utility of Fe(0)/GFH system that may be developed into a viable technology for removal of nitrate from groundwater.

Nitrate and ammonium ions removal from groundwater by a hybrid system of zero-valent iron combined with adsorbents.

Nitrate (NO(3)(-)) is a commonly found contaminant in groundwater and surface water. It has created a major water quality problem worldwide. The laboratory batch experiments were conducted to investigate the feasibility of HCl-treated zero-valent iron (Fe(0)) combined with different adsorbents as hybrid systems for simultaneous removal of nitrate (NO(3)(-)) and ammonium (NH(4)(+)) ions from aqueous solution. The maximum NO(3)(-) removal in combined Fe(0)-granular activated carbon (GAC), Fe(0)-filtralite and Fe(0)-sepiolite systems was 86, 96 and 99%, respectively, at 45 °C for 24 h reaction time. The NO(3)(-) removal rate increased with the increase in initial NO(3)(-) concentration. The NO(3)(-) removal efficiency by hybrid systems was in the order of sepiolite > filtralite > GAC. The NH(4)(+) produced during the denitrification process by Fe(0) was successfully removed by the adsorbents, with the removal efficiency in the order of GAC > sepiolite > filtralite. Results of the present study suggest that the use of a hybrid system could be a promising technology for achieving simultaneous removal of NO(3)(-) and NH(4)(+) ions from aqueous solution.

The effects of pH, bromide and nitrite on halonitromethane and trihalomethane formation from amino acids and amino sugars.

In this study, the effects of pH, bromide and nitrite on the formation of halonitromethanes (HNMs) and trihalomethanes (THMs) from eight amino acids (glycine, alanine, serine, cysteine, aspartic acid, glutamic acid, lysine and histidine) and four amino sugars (glucosamine, galactosamine, N-acetylglucosamine and N-acetylneuraminic acid) were examined for chlorination and ozonation followed by chlorination. During ozonation-chlorination, two amino acids, glycine and lysine, exhibited distinctly higher HNM formation than the other compounds. The formation of HNMs was higher at pH 8 than 6. Glycine and lysine also produced higher levels of THMs than the other compounds at pH 8. The presence of nitrite resulted in an increase in HNM formation. The presence of bromide increased the HNM formation, especially brominated HNM species. Bromine incorporation factors of trihalogenated HNMs were higher than those of THMs. For chlorination alone, HNM levels were about the detection limit (4 nM or 0.7 µg L(-1)) at pH 6 and 8, and in the presence of bromide or nitrite. Amino acids and amino sugars tested, except glycine and lysine, showed relatively low levels of THM (~15 µg L(-1)) formation.

Removal of nitrate and ammonium ions from livestock wastewater by hybrid systems composed of zero-valent iron and adsorbents.

The feasibility of hybrid systems for simultaneous removal of nitrate (NO3-) and ammonium ions (NH4+) from livestock wastewater was examined in batch experiments. As a part of efforts to remove nitrate and ammonium simultaneously, Fe0 and adsorbents including coconut-based granular activated carbon (GAC), sepiolite and filtralite were used. Various parameters such as adsorbent dosages and temperature were studied. Removal of NO3- increased with increase in temperature. Maximum NO3- removal (85.3%) was observed for the Fe0-filtralite hybrid system at 45 degrees C for a 24 h reaction time. Increase in GAC and sepiolite dosages had significant (P < 0.01) effect on the NH4+ removal efficiency, which was primarily due to the net negative surface charge of the adsorbents. The efficiency of hybrid systems for the removal of NO3- was in the order of filtralite > sepiolite > GAC, and the order of the removal of NH4+ was GAC > sepiolite > filtralite. The results of the present study suggest that the use of hybrid systems could be a promising innovative technology for achieving simultaneous removal of NO3- and NH4 from livestock wastewater.

The role of clay minerals in the reduction of nitrate in groundwater by zero-valent iron.

Bench-scale batch experiments were performed to investigate the feasibility of using different types of clay minerals (bentonite, fuller's earth, and biotite) with zero-valent iron for their potential utility in enhancing nitrate reduction and ammonium control. Kinetics experiments performed with deionized water (DW) and groundwater (GW) revealed nitrate reduction by Fe(0) proceeded at significantly faster rate in GW than in DW, and such a difference was attributed to the formation of green rust in GW. The amendment of the minerals at the dose of 25 g L(-1) in Fe(0) reaction in GW resulted in approximately 41%, 43%, and 33% more removal of nitrate in 64 h reaction for bentonite, fuller's earth, and biotite, respectively, compared to Fe(0) alone reaction. The presumed role of the minerals in the rate enhancement was to provide sites for the formation of surface bound green rust. Bentonite and fuller's earth also effectively removed ammonium produced from nitrate reduction by adsorption, with the removal efficiencies significantly increased with the increase in mineral dose above 5:1 Fe(0) to mineral mass ratio. Such a removal of ammonium was not observed for biotite, presumably due to its lack of swelling property. Equilibrium adsorption experiments indicated bentonite and fuller's earth had maximum ammonium adsorption capacity of 5.6 and 2.1 mg g(-1), respectively.

Effect of amorphous silica and silica sand on removal of chromium(VI) by zero-valent iron.

The effect of two surfaces (amorphous silica and silica sand) on the reduction of chromium(VI) by zero-valent iron (Fe(0)) was investigated using batch reactors. The amendment of both surfaces significantly increased the rate and extent of Cr(VI) removal. The rate enhancement by amended surfaces is presumed to result from scavenging of Fe(0)-Cr(VI) reaction products by the provided surfaces, which minimized surface deactivation of Fe(0). The rate enhancing effect was greater for silica compared to sand, and the difference is attributed to silica's higher surface area, greater affinity for reaction products and pH buffering effect. For a given mass of Fe(0), the reactivity and longevity of Fe(0) to treat Cr(VI) increased with increasing dose of silica. Elemental analyses of the reacted iron and silica revealed that chromium removed from the solution was associated with both surfaces, with its mass distribution being approximately 1:1 per mass of iron and silica. The overall result suggests reductive precipitation was a predominant Cr(VI) removal pathway, which involves initial reduction of Cr(VI) to Cr(III), followed by formation of Cr(III)/Fe(III) hydroxides precipitates.

Reduction of chlorinated ethanes by nanosized zero-valent iron: kinetics, pathways, and effects of reaction conditions.

Nanosized iron (< 100 nm in diameter) was synthesized in the laboratory and applied to the reduction of eight chlorinated ethanes (hexachloroethane (HCA), pentachloroethane (PCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1,1-trichloroethane (1,1,1-TCA), 1,2-dichloroethane (1,2-DCA), and 1,1-dichloroethane (1,1-DCA)) in batch reactors. Reduction of 1,1,1-TCA increased linearly with increasing iron loading between 0.01 and 0.05 g per 124 mL solution (0.08-0.4 g/L). Varying initial concentrations of PCA between 0.025 and 0.125 mM resulted in relatively constant pseudo-first-order rate constants, indicating PCA removal conforms to pseudo-first-order kinetics. The reduction of 1,1,2,2-TeCA decreased with increasing pH; however, dehydrohalogenation of 1,1,2,2-TeCA became important at high pH. All chlorinated ethanes except 1,2-DCA were transformed to less chlorinated ethanes or ethenes. The surface-area-normalized rate constants from first-order kinetics analysis ranged from < 4 x 10(-6) to 0.80 L m(-2) h(-1). In general, the reactivity increased with increasing chlorination. Among tri- and tetrasubstituted compounds, the reactivity was higher for compounds with chlorine atoms more localized on a single carbon (e.g., 1,1,1-TCA > 1,1,2-TCA). Reductive beta-elimination was the major pathway for the chlorinated ethanes possessing alpha,beta-pairs of chlorine atoms to form chlorinated ethenes, which subsequently reacted with nanosized iron. Reductive alpha-elimination and hydrogenolysis were concurrent pathways for compounds possessing chlorine substitution on one carbon only, forming less chlorinated ethanes.

Removal characteristics of trace compounds of landfill gas by activated carbon adsorption.

The removal characteristics of trace compounds and moisture in raw landfill gas (LFG) were studied. The LFG from the extraction well was saturated with water and moisture was eliminated by physical methods including cyclone-type dehydrator and compressor. The moisture removal efficiency of dehydrator and compressor was above 80%. As the moisture contents of LFG decreased, the toxic compounds like aromatics and chlorinated compounds were effectively removed by using the granular activated carbon. The breakthrough time and adsorption capacity of benzene, toluene, and ethyl benzene decreased rapidly when the relative humidity is over 60%. The effect of moisture was more pronounced at lower adsorbate concentrations tested than at higher concentrations. The breakthrough curves for multi-component mixtures show displacement effects. In the course of competing adsorption, adsorbates with strong interaction force to displace weakly bounded substances. Adsorption by activated carbon is in descending order of xylene, ethylbenzene, toluene, tri or tetrachloroethylene, benzene, carbon tetrachloride and chloroform in LFG, respectively.