Fluorine contamination, mobility, and risks in soils at a phosphate-gypsum waste landfill: a new analytical method and comparison with previous methods.

This study used a new X-ray fluorescence (XRF)-based analytical method with better precision and sensitivity to evaluate the fluorine concentrations in soil. It was hypothesized that the XRF method with a pellet-synthesizing procedure may effectively analyze the fluorine concentrations in soil with ease and reliability. The total fluorine concentrations determined using XRF were compared with those determined using three different types of analytical protocols-incineration/distillation, alkaline fusion, and aqua regia extraction procedures. Among the three procedures, the incineration/distillation procedure did not show reliable precision and reproducibility. In contrast, the total fluorine concentrations determined using the XRF analysis were linearly correlated with those determined using the alkaline fusion and aqua regia extraction procedures. Based on the results of the Korean waste leaching procedure and toxicity characteristics leaching procedure, the leachability of fluorine from soil and waste was not directly related to total fluorine concentrations in soil. Risk assessment also revealed that the fluorine-rich soils did not show non-carcinogenic toxic effects, despite exceeding the regulation level (800 mg/kg) in South Korea for total fluorine concentrations in soil. Our results suggest that XRF analysis in combination with the newly developed pretreatment method may be a promising alternative procedure for easily and rapidly determining the total fluorine concentration in soil. However, further efforts are needed to evaluate fluorine leachability and its associated risks in fluorine-contaminated soils.

Energy recovery and waste treatment using the co-pyrolysis of biomass waste and polymer.

The pyrolysis of spent coffee grounds (SCG) and polymers was examined as a waste treatment option for energy recovery and carbon sequestration. Rice straw-derived biochar was used as control biochar to evaluate the sorption capacity and energy production capability of SCG-derived biochar. SCG are characterised by high levels of volatile matter, rendering them suitable as an energy source. SCG were converted to biochar, bio-oil, and syngas via pyrolysis, with yields of 22%, 33%, and 45%, respectively. The high heating value (HHV) of the biochar and bio-oil was 20.6 and 22.9 MJ kg-1, respectively, indicating that they could be used as supplementary fuels. Co-pyrolysis with polymers (20 v v%-1) increased the HHV of biochar. Accordingly, the maximum production of CH4 and H2 increased from 0.3 and 0.04 mmol g-1 to 3.4-6.3 and 0.8-1.3 mmol g-1, respectively. Polystyrene most strongly enhanced the yields of CH4 and H2, followed by polypropylene and polyethylene; this order was likely to be in accordance with the number of carbon and hydrogen atoms present in the monomers. Similar to rice straw-derived biochar, the biochar produced from SCG demonstrated a high sorption capacity for 2,4-dinitrotoluene and chromate due to its high carbon content and anion exchange capacity, respectively. Laboratory pot tests revealed that the coffee grounds-derived biochar was able to increase the growth of young radish. Our results suggest that the pyrolysis of SCG and polymer may be a promising option for waste treatment, energy production, and carbon sequestration.

Co-pyrolysis of rice straw with industrial wastes: Waste disposal and environmental remediation.

To reduce waste volumes and recover valuable products, char was synthesized via co-pyrolysis of rice straw (RS) with spent tires, sulfur wastes, and CO2. The inclusion of wastes and CO2 in pyrolysis of RS was hypothesized to enhance the sorption ability of char for various contaminants, including 2,4-dinitrotoluene (DNT), 2,4-dichlorophenol (DCP), lead, barium, chromate (CrO42-), and selenate (SeO42-). Using a lab-scale electrical furnace, the co-pyrolysis was conducted, and the soprtion capacity of char was evaluated via a series of batch sorption experiments. The maximum sorption capacity of spent tire-RS char for DNT was 16.8 ± 0.2 mg g-1, much higher than that of RS biochar (10.1 ± 0.3 mg g-1) due to increasing carbon content from the spent tires. The sorption of DCP to the spent tire-RS char was also enhanced via hydrophobic sorption to carbon residues, although not to the same degree of DNT due to deprotonation of the DCP. Compared with RS biochar, co-pyrolysis with raw sulfur wastes and CO2 enhanced sorption of lead, barium, and chromate, which can be attributed to increased cation and anion exchange capacities resulting from developments of oxygen or sulfur-containing functional groups. Sorption of selenate was strongly affected by pH. The results suggest that co-pyrolysis of agricultural and industrial wastes and CO2 is a promising option for the final waste disposal and the production of valuable char, which can be selectively customized for various types of contaminants as sorbents.

Environmental monitoring of toxic metals in roadside soil and dust in Ulsan, South Korea: pollution evaluation and distribution characteristics.

This study investigated toxic metal distribution in roadside soil and dust in the metropolitan city of Ulsan, South Korea, and the factors affecting distribution, using Korean waste-leaching tests, determination of total concentrations, sequential extraction, and statistical analysis. Composite grab samples were collected from high-traffic roads (7 sites), low-traffic roads (2 sites), and an uncontaminated control area (2 sites) in Ulsan. The pH of roadside soil and dust was slightly alkaline. The concentrations of copper, lead, and zinc in soil as determined by Korean waste-leaching tests decreased as soil depth increased, while those of arsenic, nickel, and chromium increased. Leaching concentrations in dust were lower than in soil, with the exception of copper. Total concentrations decreased as soil depth increased, and total concentrations of metals in dust were higher than in soil. The sampling sites that exceeded the regulation levels of soil contamination in South Korea were 7 points in topsoil, 3 points in middle soil, and 9 points in dust. TCLP tests showed that the concentrations of arsenic, cadmium, and lead in topsoil and dust at Duwang and Myeongchon intersections were higher than regulatory levels. The maximum correlation coefficient among two metals in soil and dust was 0.987 (p < 0.01), for cadmium and lead. Concentrations of cadmium, copper, arsenic, lead, nickel, and mercury, mostly from tire and brake-pad abrasion, were highly correlated. The strong positive correlation between traffic volume and metals in dust suggests that vehicle emissions may be responsible for metal contamination of soil and dust. Pollution indices of topsoil at 4 sites and all dust at 7 high-traffic sites were higher than 1.0, which is consistent with an effect of vehicle traffic on metal contamination in soil and dust.

Factors affecting the sorption of halogenated phenols onto polymer/biomass-derived biochar: Effects of pH, hydrophobicity, and deprotonation.

High-performance biochar synthesized via co-pyrolysis of a polymer and rice straw (RS) was evaluated as a sorbent for ionizable halogenated phenols. Compared with RS-derived biochar, the sorption of 2,4-dichlorophenol (DCP), 2,4-dibromophenol (DBP), and 2,4-difluorophenol (DFP) onto polymer/RS-derived biochar was significantly enhanced by the properties of biochar changing due to polymer residues. According to Langmuir sorption isotherm model maximum sorption capacities for DCP, DBP, and DFP were 25.5-27.8, 22.1-26.5, and 11.5-13.3 mg/g, respectively, 3-5 times higher than those of RS-derived biochar. The removal of the polymer residues and increasing aromaticity of polymer/RS-derived biochar at elevated pyrolysis temperatures affected the sorption capacity of halogenated phenols. The surface charge of biochar and deprotonation of the halogenated phenols according to the solution pH were other factors responsible for sorption onto polymer/RS-derived biochar. Competition with other halogenated phenols, Zn2+, and Cu2+ implied that similar sorption mechanisms existed and that surface complexation and electron donor-acceptor interactions were involved in sorption onto polymer/RS-derived biochar. Our results suggest that co-disposal of thermoplastic and biomass wastes through pyrolysis may be an effective option to produce high-performance upgraded biochar as a sorbent for various types of contaminants.

Distribution, toxicity, and origins of polycyclic aromatic hydrocarbons in soils in Ulsan, South Korea.

This study was conducted to investigate the concentrations, distributions, toxicities, and sources of polycyclic aromatic hydrocarbons (PAHs) in the soils from different areas in Ulsan, South Korea. Samples were collected from 41 sites, including a waste treatment facilities area (WA), traffic facilities area (TA), child playground area (CA), industrial area (IA), railroad facilities area (RA), ore and iron scraps fields area (OA), and residential area (ReA). Ulsan was chosen for research area because it used to be an environmental hot spot in South Korea, and 16 PAHs in the US EPA priority pollutant list were selected. The concentration of total PAHs (t-PAHs) ranged from 61.7 to 12,421 µg/kg, and the average concentration of t-PAHs was 706.9 µg/kg. The distribution of PAHs by ring number indicated that the portion followed the order of 4 rings > 5 rings > 3 rings > 6 rings > 2 rings. According to PAH origin indices, LMW/HMW (low molecular weight 2-3 ring PAHs over high molecular weight 4-6-ring PAHs), phenanthrene/anthracene ratio and fluoranthene/pyrene ratio, benzo(g,h,i)perylene/indeno (1,2,3-c,d)pyrene ratio, vehicular emissions, and the combustion of fossil fuel were the sources of PAHs. The strong correlation (R2 = 0.995) between t-PAHs and total carcinogenic PAHs (t-PAHcarc) indicated that the concentration of t-PAHcarc increased in proportion with that of t-PAHs. The toxic equivalent concentrations (TEQs) of PAHs in the soils ranged from 44.0 to 1929.9 µg TEQ/kg. It is imperative to set regulatory levels for PAHs for periodic monitoring and rapid remediation action of contaminated soils, because there are no national standards in South Korea for 15 PAHs with the exception of benzo(a)pyrene.

Sorption of Nitro Explosives to Polymer/Biomass-Derived Biochar.

Factors affecting the sorptive removal of nitro explosives (2,4,6-trinitrotoluene [TNT] and hexahydro-1,3,5-trinitro-1,3,5-triazine [RDX]) to polymer/biomass-derived biochar were investigated through batch experiments. Compared with that of rice ( L.) straw (RS)-derived biochar, the sorption of TNT and RDX to polymer/RS-derived biochar was greatly enhanced by >2.5 and 4 times, respectively. The type and amount of polymer did not significantly affect the sorption of nitro explosives to polymer/RS-derived biochar. Pyrolysis temperature did not affect the sorption capacity. Surface treatment with acid or an oxidant did not significantly change the sorption capacity, suggesting that polymer residues may be strongly responsible for the enhancement. Possible polymer residues were identified via gas chromatography mass spectrometry analysis. The toxicity characteristic leaching procedure and Microtox bioassay analyses indicated that polymer/RS-derived biochar did not show possible harmful effects. Our results suggest that polymer/RS-derived biochar can be effectively used as a sorbent to remove nitro explosives both in the natural environment and engineered systems.

Biochar Amendment for Reducing Leachability of Nitro Explosives and Metals from Contaminated Soils and Mine Tailings.

The mobility and bioavailability of nitro explosives (2,4-dinitrotoluene [DNT], 2,4,6-trinitrotoluene [TNT], and hexahydro-1,3,5-trinitro-1,3,5-triazine [RDX]) in biochar-amended soils and toxic metals (As, Cd, Cu, Pb, and Zn) in biochar-amended mine tailings were investigated via various types of leaching procedures in laboratory-scale batch experiments. The results from the toxicity characteristic leaching procedure (TCLP) and hydroxypropyl-ß-cyclodextrin (HPCD) extraction showed that approximately 55 to 95% of the explosives were released from the contaminated soils and would thus be considered as mobile. With the addition of biochar, the extracted concentrations of explosives were reduced to less than 10% of the initial concentrations after 10 d. According to the results from a Korean waste leaching method, the TCLP method, and diethylenetriaminepentaacetic acid (DTPA) extraction, adding biochar to mine tailings reduced the extractability and bioavailability of metals. The chemical forms of the metals, types of extractants, pH, and curing period strongly affected the extractability of metals from mine tailings. The results suggest that biochar is a promising immobilizer of explosives and metals in contaminated soils and mine tailings under limited conditions.

Factors affecting sorption of nitro explosives to biochar: pyrolysis temperature, surface treatment, competition, and dissolved metals.

The application of rice straw-derived biochar for removing nitro explosives, including 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), from contaminated water was investigated through batch experiments. An increase in the pyrolysis temperature from 250 to 900°C in general led to higher pH, surface area, cation exchange capacity (CEC), point of zero charge, and C:O ratio of biochar. The maximum sorption capacity estimated by a mixed sorption-partition model increased when pyrolysis temperatures were elevated from 250 to 900°C, indicating that C content and aromaticity of biochar were strongly related to the sorption of nitro explosives to biochar. Surface treatment with acid or oxidant increased the sorption capacity of biochar for the two strong π-acceptor compounds (DNT and TNT) but not for RDX. However, the enhancement of sorption capacity was not directly related to increased surface area and CEC. Compared with single-sorption systems, coexistence of explosives or cationic metals resulted in decreased sorption of each explosive to biochar, suggesting that sorption of nitro explosives and cationic metals to electron-rich portions in biochar was competitive. Our results suggest that π-π electron donor acceptor interactions are main sorption mechanisms and that changing various conditions can enhance or reduce the sorption of nitro explosives to biochar.

Sorptive removal of nitro explosives and metals using biochar.

The feasibility of using biochar as a sorbent to remove nitro explosives and metals from contaminated water was investigated through batch experiments. Biochar, synthesized using various biomasses, showed a porous structure and a high surface area and includes embedded carbonate minerals. Compared with granular activated carbon, biochar was competitive as a sorbent for removing Cd, Cu, Pb, and Zn from water according to the maximum sorption capacities of the metals. Some biochars also effectively sorbed nitro explosives from water. Correlation analysis between maximum sorption capacities and properties of biochar showed that the sorption capacity of biochar for cationic toxic metals is related to cation exchange capacity and that the sorption capacity of explosives is proportional to surface area and carbon content. Results from X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses and laboratory experiments suggest that surface functional groups may be responsible for the sorption of cationic metals to the biochar surface. In contrast, carbon contents may account for the sorption of explosives, possibly through π-π electron donor-acceptor interactions. Our results suggest that biochar can be an attractive and alternative option in environmental remediation of nitro explosives and metals through sorption and immobilization and that appropriate selection of biochar may be necessary according to the types of contaminant and the properties of biochar.

Biodegradable dust suppressants prepared from biomass-based materials: The role of viscosity and suppressed particles.

In this study, biodegradable dust suppressants were prepared using glycerol and biomass-based oily compounds, including palm oil, biodiesel, and soybean oil. The suppressing ability of the glycerol and the oily compound mixture was evaluated using wind tunnel tests, and factors affecting the suppression of the particles were determined. The replacement of sodium dodecyl sulfate with coco glucoside and lauryl glucoside significantly enhanced the biodegradability of the suppressants (2.02 vs. 9.01 and 8.54 mg/L of BOD5). The glycerol and soybean oil mixture exhibited excellent performance owing to the relatively high viscosity of the suppressants, and the optimal dilution ratio was 1:50 and 1:1000 for sand and granite-weathered soil, respectively. More than 98% of suppression was obtained under the optimal conditions. The effect of the particle properties (particularly permeability) was significant, even though the viscosity of the suppressants was responsible for the suppression of the particles. Our results suggest that the mixture of glycerol and biomass-based oily compounds could be a promising suppressant for reducing the mobility of ultrafine particles in the atmosphere.Implications: Since the early 2010s, anthropogenic fugitive dust from industrial activities has become a serious environmental issue due to its serious hazards to the environment and human health in South Korea. So far, several dust suppressants (mostly salts) were made and used for field application. However, due to their toxic effects, it is necessary to develop a new eco-friendly suppressant that can be biodegraded in the soil and that is not hazardous to human health or the environment. Previously we have developed an eco-friendly dust suppressant with low toxicity and high suppression ability using ingredients and by-products of biodiesel production, marine biomass, and commercial vegetable oils (Tsgot and Oh 2021, J. Air Waste Manag. Assoc. 71:1386-1396). However, due to the low biodegradability of surfactant, the synthesized dust suppressants showed limited biodegradability. As a follow-up to our previous study, we employed readily biodegradable surfactants as additives to enhance the biodegradability of the dust suppressants with the same excellent suppressing ability. To determine the optimal conditions, the synthesis and preparation of the dust suppressants was conducted using biodegradable surfactants, including coco glucoside and lauryl glucoside. The factors affecting the suppressing ability of the suppressants were examined via wind tunnel tests. These factors include the dilution factors, the viscosity of the suppressants, and the type of suppressed particles. Possible suppressing mechanisms were also discussed.

Black carbon-mediated reduction of 2,4-dinitrotoluene by dithiothreitol.

By using various types of black carbon (BC), including chemically converted graphene (CCG), multiwalled carbon nanotubes (MWCNT), and granular activated carbon (GAC), BC-mediated reduction was investigated with 2,4-dinitrotoluene (DNT), a model nitroaromatic compound. We hypothesized that by providing sorption and electron transfer sites, BC can be used as a catalyst to accelerate DNT reduction by dithiothreitol (DTL), a thiol reductant. Results from batch experiments showed that CCG, MWCNT, and GAC could promote reduction of DNT by DTL. The yield ratio of the two aminonitro intermediates was approximately 1:1, which was consistent with that in a graphite system. However, fullerene did not significantly enhance the reduction of DNT, likely due to being a π acceptor. Kinetic data analysis showed that removal of DNT in the presence of BC and DTL was linearly proportional to the electrical conductivity of BC, suggesting that the graphitic structure of BC may be responsible for DNT removal. Our results indicate that the presence of BC materials may affect the fate of nitroaromatic compounds under electron-rich conditions.

Degradation of phenol by perborate in the presence of iron-bearing and carbonaceous materials.

We investigated the oxidation of phenol by perborate-a newly proposed oxidant-in the presence of iron-bearing and carbonaceous materials through batch experiments. We hypothesized that the oxidation of phenol by perborate was enhanced due to the formation of reactive oxygen species (ROS) in the presence of iron-bearing or carbonaceous materials. Zero-valent iron and ferrous iron (Fe2+) promoted the oxidation of phenol by perborate. Biochar, granular activated carbon, an anode carbonaceous material recovered from a spent Li-ion battery, and graphite also accelerated the oxidation of phenol by perborate. Quenching experiments with radical scavengers and electron paramagnetic resonance (EPR) analysis revealed that hydroxyl (˙OH) and superoxide (O2˙-) radicals were generated and enhanced the degradation of phenol in the perborate systems. Singlet oxygen (1O2) was involved in the iron-bearing material-perborate systems. Moreover, we found that Persil®, a commercial perborate detergent, enhances the oxidation of phenol in the presence of iron-bearing and carbonaceous materials. Our results suggest that perborate can be used for advanced oxidation processes to remediate recalcitrant organic contaminants in natural environments and engineered systems.

Changes in the sorption and rate of 17ß-estradiol biodegradation by dissolved organic matter collected from different water sources.

The potential biodegradation and subsequent transformation of 17ß-estradiol (E2) to estrone (E1) were examined in the presence of various dissolved organic matter (DOM) isolated from effluent, river and lake waters. In addition, estrogenicity was estimated in association with the removal of E2 via its sorption onto DOM and biodegradation. The more biodegradable lake-derived DOM promoted more extensive transformation of E2 into E1 than the effluent organic matter through a biodegradation process. Overall, under all conditions, biodegradation dominated the removal of E2 in water. The increased dissolved organic carbon (DOC) concentrations in river and lake-derived DOM (e.g. 6.5 mg C L(-1)) reduced the removal of E2 by decreasing its biodegradation due to the moderate sorption of E2 onto DOM. The effluent organic matter showed greater removal of E2 via biodegradation, as well as significantly high sorption. This was associated with a large amount of hydrophobic fulvic acid (FA)- and humic acid (HA)-like organic components, as shown by the small increase in the specific UV absorbance at 254 nm (SUVA(254)). An increase in the DOC concentration reduced the removal of E2, resulting in high estrogenicity. The present study suggests that both organic composition and DOC concentration influenced the removal of E2 and, therefore, should be fully considered when assessing estrogenicity and its impacts on the aquatic environment.

The role of black carbon as a catalyst for environmental redox transformation.

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983-6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC--graphite, activated carbon, and diesel soot--to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H(2)S. All three types of BC enhanced DNT and DBP reduction. H(2)S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.

Preparations and application of dust suppressants from biomass-based materials.

Both natural and anthropogenic fugitive dust can cause serious hazards to the environment and human health. In this study, the development of biodegradable dust suppressants and their environmental impacts were evaluated. Biodegradable dust suppressants were prepared using various biomass-based polymeric materials such as crude glycerol (a by-product of biodiesel manufacturing), biodiesel, palm oil, cooking oil, seaweed mixtures, wakame (Undaria pinnatifida), and red algae. The results of wind-tunnel tests with Korean standard sand demonstrated that spraying diluted mixtures of crude glycerol and biomass materials can significantly reduce the generation of dust. The optimal molar mixing ratio of crude glycerol and the biomass materials was 1:1, and the optimal dilution concentration was determined to be 100 times for the mixture of crude glycerol and biodiesel, palm oil, and cooking oil and 50 times for the mixture of crude glycerol with a seaweed mixture, wakame, and red algae. The suppression ability was 83.4%, 60.4%, 99.5%, and 98.1% for the mixtures of glycerol with soybean oil, palm oil, wakame, and red algae, respectively. The mixtures of glycerol plus wakame or red algae were the most efficient suppressants; they also have substantial biodegradability. Our results suggest that the mixture of crude glycerol with the various oils or the seaweeds may be a promising option to develop nontoxic biodegradable dust suppressants.Implications: Since the early 2010s, anthropogenic fugitive dust from industrial activities has become a serious environmental issue due to its serious hazards to the environment and human health in South Korea. The origin and responsibility of the dusts is still disputable to prepare appropriate actions to take, which could be solved by scientific collaboration with surrounding countries. Regardless, domestic efforts to reduce the generation of fine dust from various sources should also be made. So far, several dust suppressants (mostly salts) were made and used for field application. However, due to their toxic effects, it is necessary to develop a new eco-friendly suppressant that can be biodegraded in the soil and that is not hazardous to human health or the environment. In this study, we try to develop an eco-friendly dust suppressant with low toxicity, to evaluate various potential dust suppressants, and to propose promising candidate products for commercialization and mass production. Ingredients and by-products of biodiesel production, marine biomass, and commercial vegetable oils were selected for the synthesis of suppressants. The optimal mixing ratio was determined, and the suppression ability was evaluated via wind tunnel tests. Considering biodegradability, the most effective suppressants were determined.

Anode carbonaceous material recovered from spent lithium-ion batteries in electric vehicles for environmental application.

Recycling opportunities for graphitic carbon from lithium-ion battery (LIB) anodes have been neglected owing to the relative low value of application. In this study, the potential methods for removing toxic metals (lead, barium, and cadmium) and organic compounds (2,4-dinitrotoluene [DNT], 2,4,6-trinitrotoluene [TNT], hexahydro-1,3,5-trinitro-1,3,5-triazine [RDX], and 2,4-dichlorophenol [DCP]) with anode carbonaceous material (ACM) obtained from the anodes of spent LIBs were evaluated. The sorption ability of ACM for lead is higher (the maximal sorption capacity is 43.5 mg/g) than for barium and cadmium. Similarly, the maximal sorption capacity of ACM for DCP is 6.5 mg/g, which is higher than those for TNT and DNT (2.6 and 2.3 mg/L, respectively). As a catalyst, ACM significantly enhances oxidation by persulfate with zero-valent iron and reduction by dithiothreitol (DTT) and hydrogen sulfides for nitro compounds. In addition, the graphitic properties enhance the redox reactions. The results suggest that ACM from spent LIBs may be an effective sorbent and catalyst in redox processes for the remediation of contaminated water and soil.

FeS-biochar and Zn(0)-biochar for remediation of redox-reactive contaminants.

To enhance the removal of redox-reactive contaminants, biochars including FeS and Zn(0) were developed via pyrolysis. These biochars significantly promoted the removal of 2,4-dichlorophenol (DCP) by means of sorption and reduction. Compared to direct reduction with FeS and Zn(0), the formation of reduction intermediates and product was enhanced from 21% and 22% of initial DCP concentration to 41% and 52%, respectively. 2,4-Dinitrotoluene (DNT), chromate (CrO4 2-) and selenate (SeO4 2-) were also reductively transformed to reduction products (e.g., 2,4-diaminotoluene [DAT], Cr3+, and selenite [SeO3 2-]) after they sorbed onto the biochars including FeS and Zn(0). Mass recovery as DAT, Cr3+ and selenite was 4-20%, 1-3%, and 10-30% under the given conditions. Electrochemical and X-ray analyses confirmed the reduction capability of the biochars including FeS and Zn(0). Fe and S in the FeS-biochar did not effectively promote the reductive transformation of the contaminants. Contrastingly, the stronger reducer Zn(0) yielded faster reductive transformation of contaminants over the Zn(0)-containing biochar, while not releasing high concentrations of Zn2+ into the aqueous phase. Our results suggest that biochars including Zn(0) may be suitable as dual sorbents/reductants to remediate redox-reactive contaminants in natural environments.

Upgrading biochar via co-pyrolyzation of agricultural biomass and polyethylene terephthalate wastes.

Spent polyethylene terephthalate (PETE) bottles were collected and co-pyrolyzed with rice straw (RS) to examine the characteristics and performance of biochar as a sorbent for various types of U.S. EPA priority pollutants, including 2,4-dinitrotoluene (DNT), 2,4-dichlorophenol (DCP), Pb, chromate (CrO4 2-), and selenate (SeO4 2-). During sorption of contaminants to PETE/RS-derived biochar, PETE residues from pyrolysis, pH, and pyrolysis temperature greatly affected the sorption process. Depending on the types of contaminants and experimental conditions, co-pyrolysis of PETE and RS may enhance the sorption of contaminants through different sorption mechanisms, including hydrophobicity, electrostatic force, ion exchange, surface complexation, and surface precipitation. Unlike other contaminants, selenate was reductively transformed by delocalized electrons from the graphitic structure in biochar. Our results strongly suggest that co-pyrolysis of PETE and agricultural wastes may be favorable to enhance the properties of biochar. In addition to syn-gas and bio-oil from co-pyrolysis, biochar may be a valuable by-product for commercial use.

The effect of suspended particles coated by humic acid on the toxicity of pharmaceuticals, estrogens, and phenolic compounds.

The sorption characteristics of 10 organic chemicals, categorized as pharmaceuticals, estrogens and phenols, onto synthetic suspended particle (i.e., alumina) coated with humic acid were investigated according to their octanol-water partition coefficient (K(ow)). Chemical analyses were performed with gas chromatography and mass spectrometry (GC/MS) and high performance liquid chromatography (HPLC). The effects of particles on the toxicity reduction were evaluated using bioassay tests, using Daphnia magna and Vibrio fisheri for phenols and pharmaceuticals, and the human breast cancer cell MCF-7 for estrogens. Sorption studies revealed that 22 and 38% of octylphenol and pentachlorophenol, respectively, were removed by suspended particle, whereas 2,4-dichlorophenol was not removed, which was directly proportional to the logK(ow) value. Similar to the sorption tests, suspended particles significantly reduced the acute toxicities of octylphenol and pentachlorophenol to D. magna and V. fisheri (p<0.01), but there was no significant difference in the toxicity of 2,4-dichlorophenol to D. magna (p=0.8374). Pharmaceuticals, such as ibuprofen, gemfibrozil and tolfenamic acid, showed no discernible sorption to the suspended particle, with the exception of diclofenac, which revealed 11% sorption. For estrogens, such as estrone, 17beta-estradiol and 17alpha-ethynylestradiol, the results indicated no reduction in the sorption test. This may be attributed to the polar interaction by functional groups in sorption between pharmaceuticals and estrogens and suspended particles. In the bioassays, presence of suspended particles did not significantly modify the toxicity of pharmaceuticals (regardless of their K(ow) values) to D. magna, V. fisheri or E-screen.