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1.
Chemosphere ; 354: 141634, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38462189

RESUMO

The complexity of the subsurface contaminated by chlorinated solvents such as trichloroethylene (TCE) makes it challenging to gain a complete understanding of contamination distribution and establish a conceptual site model (CSM). High-resolution vertical contaminant concentration profiling across both the unsaturated zone and the saturated aquifer is desirable for mapping the distribution of contamination. A Fick's law-based polydimethylsiloxane (PDMS) dialysis passive sampler was developed and evaluated on a field scale for its potential application. This study tests the passive sampler at two TCE contaminated sites, and the sampling results were compared with the results from different sampling methods based on the relative percent difference. The PDMS dialysis passive sampler obtained more representative soil gas concentrations in the unsaturated zone than a portable monitoring and sampling device, which caused soil gas flow disturbance by soil gas pumping during sample collection. In the saturated aquifer sampling, the results obtained by the PDMS dialysis passive sampler correlated well with those obtained by a commercial polyethylene passive diffusion bag, and exhibited higher sensitivity under low TCE concentration conditions. Furthermore, the PDMS dialysis passive samplers were densely deployed inside each monitoring well at multiple depths, at two sites, to achieve high-resolution monitoring across the unsaturated zone and saturated aquifer. Based on the PDMS dialysis sampler data, a more comprehensive three-dimensional CSM was systematically established.


Assuntos
Tricloroetileno , Poluentes Químicos da Água , Solventes/análise , Monitoramento Ambiental/métodos , Poluentes Químicos da Água/análise , Diálise Renal , Tricloroetileno/análise , Dimetilpolisiloxanos , Solo
2.
J Hazard Mater ; 454: 131467, 2023 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-37104957

RESUMO

1,3-Dinitrobenzene (1,3-DNB) is listed by the USEPA as a priority pollutant. 1,3-DNB has two nitro functional groups (-NO2) bound to the benzene ring, with a +III nitrogen oxidation states, and strong electronegativity, and therefore can be reductively degraded by gaining electrons. Weeds that contain a high proportion of polyphenols can supply electrons and act as natural reducing agents. This study investigated the potential of various weeds to reductively remove 1,3-DNB from aqueous phase. The Taguchi L9 Orthogonal experimental design method was used to explore the optimum operational parameters. According to the analyzed characteristics of weeds, including total phenol content, antioxidant capacity, metal chelating capacity, reducing capacity, and environmental adaptability, the weed Sphagneticola trilobata, containing 11.93 mg of gallic acid equivalent per gram of weed (mg-GAE/g-weed), was selected for 1,3-DNB degradation experiments. The results showed that the optimum reaction conditions for the degradation of 1,3-DNB in the aqueous phase using Sphagneticola trilobata were: pH 3, a weed dose of 10 g/L, reaction time of 14 day, and initial 1,3-DNB concentration of 0.5 mM. According to ANOVA analysis, the weed dose was the most significant factor in the experiment, and each 1 mg of 1,3-DNB degraded required 120 mg of dry weeds.

3.
J Hazard Mater ; 439: 129657, 2022 10 05.
Artigo em Inglês | MEDLINE | ID: mdl-35905609

RESUMO

The presence of trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) in the subsurface can generate a dissolved phase plume in groundwater. This study developed an alkaline activated sodium persulfate (SPS) sustained release oxidation rod (alkaline SPS SR-Rod) for long-term in situ chemical oxidation accelerated treatment of TCE dissolved from TCE DNAPL, by creating a greater concentration gradient at the TCE DNPL boundary. The dissolution of TCE DNAPL (1 mL) in water (280 mL) generated ~700 mg L-1, with a volumetric mass transfer coefficient (kLa) of 0.0187 d-1. The alkaline SPS SR-Rod system had a kLa of 0.013 d-1 for TCE dissolution at early stage, and thereafter aqueous TCE concentration remained below ~10 mg L-1 over 60 d of reaction. An SPS SR-Rod life-span of 186 d, for 90% of SPS released from the rod, was estimated. In the soil-water system, aqueous TCE was maintained < 3 mg L- 1 throughout the reaction and the soil oxidant demand was determined to be ~4 g-SPS/kg-soil in the alkaline SPS SR-Rod system. These results revealed that the use of the alkaline SPS SR-Rod can be effective as a method of treating dissolved TCE released from DNAPL contamination, and thereby accelerating TCE DNAPL removal.


Assuntos
Água Subterrânea , Tricloroetileno , Poluentes Químicos da Água , Preparações de Ação Retardada , Compostos de Sódio , Solo , Sulfatos , Poluentes Químicos da Água/análise
4.
Chemosphere ; 286(Pt 3): 131818, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34416591

RESUMO

This study explored the potential reactivities of various reductants in inducing subsurface TCE degradation in natural soils. It was found that bisulfite (HSO3-) exhibited the ability to induce reduction in soil iron minerals, and increase the degradation of TCE in the soil slurry system; however, no TCE degradation occurred in the aqueous system. The role of TCE degradation by soil constituents, such as major soil mineral elements, Fe and humic acid (HA) on HSO3-, was examined in aqueous phase. It was seen that by themselves, the presence of Fe3+, HA, Fe2O3, FeOOH, and Fe3O4 did not result in substantial TCE removals. However, the presence of HSO3- can significantly induce iron reduction, producing a reducing condition that can result in complete TCE degradation. Furthermore, the reductive pathway was identified as the dominant degradation route via electron scavenging with periodate ion. To demonstrate the applicability of HSO3- reduction enhancement, a HSO3-/TCE mixed solution was flushed through a soil column, with gradually increased HSO3- concentrations, at a fixed flow rate, and also with varied flushing rates at a fixed HSO3- concentration. Based on our study, a 10 mM HSO3- solution may be effective for some environmental sites; however, each site requires specific evaluation based on contaminant concentrations and subsurface conditions.


Assuntos
Tricloroetileno , Poluentes Químicos da Água , Ferro , Oxirredução , Solo , Sulfitos , Tricloroetileno/análise , Poluentes Químicos da Água/análise
5.
Chemosphere ; 285: 131471, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34271463

RESUMO

A limitation of soil vapor extraction (SVE) remediation for total petroleum hydrocarbons (TPHs) in the unsaturated zone is the inability to remove the less volatile petroleum mixture compounds in diesel fuel. SVE combined with foam flushing may have the potential to enhance dissolution or mobilization of soil sorbed diesel and allow mobilized diesel to move to the SVE extraction well. A nonionic surfactant polyoxyethylene (20) sorbitan monooleate (TW80) was selected for generating foam, and a procedure to incorporate the oxidant sodium persulfate (SPS) in generating TW80/SPS foam to deliver chemical oxidation, was also studied. Both TW80 and TW80/SPS foams exhibited 96-98% quality under 8-32 mM of TW80 and 10-50 mM of SPS. The addition of SPS in TW80 solution resulted in elevated ionic content and degradation of TW80, which may reduce the foam stability and have minor effects on foam quality. Through analysis of interrelationships among column flushing experimental parameters, it was shown that the foam quality was reduced to 42-47% when foam flushed through a diesel contaminated soil column. Moreover, the results of column flushing tests operated for 12 h indicated that the effectiveness of removal of diesel by different foams followed the order of TW80 foam (53%) > TW80/SPS foam (37%) >N2 gas flow alone (3%). It was shown that foam flushing could be an alternative approach, rather than using N2 gas flow alone (SVE), in enhancing SVE for reducing diesel contamination in the unsaturated zone.


Assuntos
Recuperação e Remediação Ambiental , Petróleo , Poluentes do Solo , Biodegradação Ambiental , Gasolina , Solo , Poluentes do Solo/análise
6.
J Hazard Mater ; 401: 123387, 2021 01 05.
Artigo em Inglês | MEDLINE | ID: mdl-32763689

RESUMO

Passive sampling (PS) is a method employed to detect volatile organic compounds in groundwater and soil gas. This study attempted to manufacture a polydimethylsiloxane (PDMS) dialysis passive sampler for potential application in detecting trichloroethylene (TCE) in aqueous and gaseous phases. The equilibrium time of the passive sampler was initially determined, followed by multilayer passive sampling in a three-dimensional sandbox to construct a tomography of TCE vapor spatial distribution in the vadose zone above the saturated water level. The results indicated that an equilibrium time period of >10 d was required in the aqueous phase containing TCE concentrations ranging from 3 to 25 mg L-1, while an equilibrium time period of >12 d was necessary for TCE vapor concentrations ranging from 2.6-26 mg L-1. Therefore, a 14 d of equilibrium time was suggested for application of this passive sampler in detecting vapor and aqueous phase TCE. After collection of the passive samples from the three-dimensional sandbox, a three dimensional visualization was created, and it was demonstrated to be a reasonable way to simulate a three dimensional TCE distribution. It was confirmed that the passive sampler developed in this study is effective for assessing TCE contamination in the subsurface.

7.
Chemosphere ; 267: 129196, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33340881

RESUMO

Green tea (GT) leaves can be brewed into a solution rich in polyphenols that serve as effective reducing agents, and the complexes formed by combining green tea with ferrous ion (GT/Fe(II)) can provide an elevated reduction potential. The dissociated GT polyphenols at alkaline pH can dramatically increase the formation of GT/Fe(II) complexes. This experimental work evaluated the reductive reactivity of alkaline GT solution and GT/Fe(II) complexes (at pH 10) on 14 halogenated volatile organic compounds (VOCs). Carbon tetrachloride (CT), with a highest carbon oxidation state (COS) of IV, was observed to be degradable by the alkaline GT solution, while all others proved ineffective. The GT/Fe(II) complexes are very reactive and capable of degrading halogenated methanes, ethanes, and ethenes, in which chemical structures exhibit zero or positive COS values, and the chlorine or bromine atom is bonded at the saturated carbon atom, such as CT, chloroform, bromoform, dibromomethane, 1,1,1-trichloroethane, and 1,1,1,2-tetrachloroethane. The linear free energy relationship (LFER) approach was used to determine the overall reduction potentials (EH0) of the alkaline GT solution and GT/Fe(II) complexes, which were found to be -0.131 V and -0.368 V, respectively. These findings demonstrated that GT/Fe(II) complexes exhibit the potential to remediate halogenated contaminants and the EH0 information obtained in this study may serve as a reference in determining probable reactivity that contributes to degradation of environmental contaminants.


Assuntos
Ferro , Chá , Tetracloreto de Carbono , Oxirredução , Solventes
8.
Chemosphere ; 232: 281-286, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31154189

RESUMO

The environmental persistence of hazardous organochlorine pesticides (OCPs) such as lindane has resulted in a need for the development of reliable remediation technology for the removal of OCPs. Green tea extract/Fe2+ under alkaline conditions is a potential green chemistry technology proven to be effective in reducing lindane. This study investigated the feasibility of directly using green tea leaves (GT-leaf) or cold-brew tea solution (GT-sol) with Fe2+ additives at (bi)carbonate buffered pH 10 to treat lindane in the aqueous phase. The polyphenol was gradually released in the GT-leaf system and reached a similar concentration as that in the GT-sol system (∼800 mg L-1 at pH 6.5). Based on the analytical results of lindane degradation byproducts, it was recognized that the reductive mechanism acts as a major pathway and alkaline hydrolysis is a minor pathway. However, physical adsorption rapidly removes lindane from the GT-leaf system. A comprehensive evaluation of lindane degradation, chlorobenzene formation, degradation kinetics, and chloride liberation were conducted for the alkaline GT-sol/Fe2+ system. The nonlinear simulations of the models developed showed good fits, with R2 > 0.96. This study highlights the potential for GT-sol/Fe2+ systems to remediate OCPs contamination.


Assuntos
Hexaclorocicloexano/química , Chá/química , Adsorção , Poluentes Ambientais , Hexaclorocicloexano/análise , Hidrocarbonetos Clorados/análise , Hidrocarbonetos Clorados/química , Cinética , Praguicidas/análise , Praguicidas/química , Folhas de Planta/química
9.
Chemosphere ; 198: 297-302, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29421742

RESUMO

The use of a dual oxidation system, which combines sodium persulfate (Na2S2O8, SPS) and hydrogen peroxide (H2O2, HP) is increasing as an in-situ chemical oxidation (ISCO) process for soil and groundwater remediation. An analytical method was assessed in this study for determining individual oxidant concentration in order to understand the interactions, and variations in the concentrations, of SPS and HP in aqueous systems containing both SPS and HP. The iodometric titration method was demonstrated to be capable of measuring total oxidant (SPS + HP) concentration; while the ceric sulfate titration method can be used specifically for measuring HP in the dual oxidation system without interfering with the iodometric titration. Therefore, SPS concentration can be deduced by subtraction of the HP concentration from the total oxidant concentration. Direct iodometric titration for determination of total oxidant at concentration above 20 mM exhibited <8% concentration. Based on the results of indirect determination of SPS in the dual oxidation system, an approximate 10% concentration variation was expected. This research may serve as a reference for measuring oxidant variations in this ISCO dual oxidant application.


Assuntos
Recuperação e Remediação Ambiental/métodos , Peróxido de Hidrogênio/química , Compostos de Sódio/química , Sulfatos/química , Fracionamento Químico/métodos , Água Subterrânea/química , Oxidantes/química , Oxirredução , Solo/química , Poluentes do Solo/análise , Poluentes do Solo/química , Poluentes da Água/química
10.
Chemosphere ; 193: 438-446, 2018 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-29154119

RESUMO

To take advantage of the road pavement network where non-point source (NPS) pollution such as benzene, toluene, ethyl-benzene, and xylene (BTEX) from vehicle traffic exhaust via wet and dry atmospheric deposition occurs, the asphalt pavement may be used as a media to control the NPS pollution. An experiment to prepare an adsorptive porous reactive pavement (PRP) was initiated to explore the potential to reduce environmental NPS vehicle pollution. The PRP was prepared and studied as follows: various activated carbons (AC) were initially screened to determine if they were suitable as an additive in the porous asphalt mixture; various mixtures of a selected AC were incorporated with the design of porous asphalt concrete (PAC) to produce PRP, and the PRP formulations were tested to ensure that they comply with the required specifications; qualified specimens were subsequently tested to determine their adsorption capacity for BTEX in aqueous solution, as compared to conventional PAC. The PRP08 and PRP16 samples, named for the design formulations of 0.8% and 1.6% of AC (by wt. in the formulation), exhibited low asphalt drain-down and low abrasion loss and also met all regulated specifications. The BTEX adsorption capacity measurements of PRP08 and PRP16 were 33-46%, 36-51%, 20-22%, and 6-8% respectively, higher than those obtained from PACs. Based on the test results, PRPs showed good physical performance and adsorption and may be considered as a potential method for controlling the transport of NPS vehicle pollutants.


Assuntos
Carvão Vegetal/química , Poluição Ambiental/prevenção & controle , Hidrocarbonetos/química , Emissões de Veículos , Adsorção , Benzeno , Derivados de Benzeno , Poluição Ambiental/análise , Porosidade , Tolueno , Xilenos
11.
Artigo em Inglês | MEDLINE | ID: mdl-28494219

RESUMO

Tetramethylammonium hydroxide (TMAH) is widely used in high-tech industries as a developing agent. Ultraviolet (UV) light-activated persulfate (PS, S2O82-) can be used to generate strongly oxidative sulfate radicals, and it also exhibits the potential to treat TMAH-containing wastewater. This study initially investigated the effect of S2O82- concentration and UV strength on the UV/S2O82- process for the degradation of TMAH in a batch reactor. The results suggested that 15 watts (W) of UV-activated S2O82- at concentrations of 10 or 50 mM resulted in pseudo-first-order TMAH degradation rate constants of 3.1-4.2 × 10-2 min-1, which was adopted for determining the hydraulic retention time (HRT) in a continuous stirred tank reactor (CSTR). The operating conditions (15 W UV/10 mM S2O82-) with a HRT of 129 min resulted in stable residual concentrations of S2O82- and TMAH at approximately 2.6 mM and 20 mg L-1 in effluent, respectively. Several TMAH degradation intermediates including trimethylamine, dimethylamine, and methylamine were also detected. The effluent was adjusted to a neutral pH and evaluated for its biological acute toxicity using Cyprinus carpio as a bioassay organism. The "bio-acute toxicity unit" (TUa) was determined to be 1.41, which indicated that the effluent was acceptable for being discharged into an aquatic ecosystem.


Assuntos
Compostos de Amônio Quaternário/análise , Sulfatos/química , Raios Ultravioleta , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Animais , Carpas/crescimento & desenvolvimento , Desenho de Equipamento , Dose Letal Mediana , Oxirredução , Compostos de Amônio Quaternário/efeitos da radiação , Compostos de Amônio Quaternário/toxicidade , Taiwan , Testes de Toxicidade Aguda , Poluentes Químicos da Água/efeitos da radiação , Poluentes Químicos da Água/toxicidade , Purificação da Água/instrumentação
12.
Chemosphere ; 166: 482-488, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27705834

RESUMO

Nitro-aromatic compounds (NACs) such as 1,3-dinitrobenzene (1,3-DNB) contain the nitrogroup (-NO2), in which the N with a +III oxidation state accepts electrons. Water soluble ascorbic acid (AsA) at elevated pH produces electron transfer and governs the electron-donating pathway. The influence of the NaOH/AsA molar ratio on the degradation of 1,3-DNB was investigated. Using 0.21-2 M NaOH and 20-100 mM AsA, nearly complete 1,3-DNB removals (90-100%) were achieved within 0.5 h. On the basis of intermediates identified using GC/MS, the reduction pathways of 1,3-DNB can be categorized into step-by-step electron transfer, and condensation routes. A higher NaOH/AsA molar ratio would result in relatively higher AsA decomposition, promote the condensation route into the formation of azo- and azoxy-compounds, and ultimately reduce 1,3-DNB to 1,3-phenylenediamine. Contaminated soil flushing using 500 mM NaOH/100 mM AsA revealed that 1,3-DNB was completely degraded within 2 h. Based on these test results, the alkaline AsA treatment method is a potential remediation process for NACs contaminated soils.


Assuntos
Ácido Ascórbico/química , Dinitrobenzenos/química , Hidróxido de Sódio/química , Elétrons , Recuperação e Remediação Ambiental , Concentração de Íons de Hidrogênio , Nitrocompostos/química , Oxirredução , Fenilenodiaminas/química , Poluentes do Solo/química , Água , Poluentes Químicos da Água/química
13.
Chemosphere ; 147: 82-7, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26761601

RESUMO

Generally, molybdenum (Mo) metals in the environment are very rare, but wastewater discharges from industrial processes may contain high concentrations of Mo, which has the potential to contaminate water or soil if not handled properly. In this study, the impact of three common compounds of hexavalent Mo (sodium molybdate (Na2MoO4‧2H2O), ammonium molybdate ((NH4)6Mo7O24‧4H2O) and molybdenum trioxide (MoO3)) in an aquatic system were assessed based on 48-h exposure acute toxicity to Daphnia magna (D. magna). The LC50 toxicities for associated conjugate ions including Na(+), Cl(-), SO4(2-), and NH4(+) were determined. Furthermore, the LC50 values for the three forms of hexavalent Mo were determined, and the acute toxicities of the Mo forms were found to follow the order: (NH4)6Mo7O24‧4H2O > MoO3 > Na2MoO4‧2H2O in solution. (NH4)6Mo7O24‧4H2O exhibited the lowest LC50 of 43.3 mg L(-1) (corresponding to 23.5 mg Mo L(-1)) among the three molybdenum salts. The research confirmed that the toxicity of molybdenum in the aquatic system is highly dependent on the form of molybdenum salts used, and is also associated with the influence of the background water quality.


Assuntos
Daphnia/efeitos dos fármacos , Molibdênio/toxicidade , Óxidos/toxicidade , Poluentes Químicos da Água/toxicidade , Animais , Dose Letal Mediana
14.
J Hazard Mater ; 302: 137-143, 2016 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-26453825

RESUMO

Alkaline ascorbic acid (AA) exhibits the potential to reductively degrade nitrobenzene (NB), which is the simplest of the nitroaromatic compounds. The nitro group (NO2(-)) of NB has a +III oxidation state of the N atom and tends to gain electrons. The effect of alkaline pH ranging from 9 to 13 was initially assessed and the results demonstrated that the solution pH, when approaching or above the pKa2 of AA (11.79), would increase reductive electron transfer to NB. The rate equation for the reactions between NB and AA at pH 12 can be described as r=((0.89±0.11)×10(-4) mM(1-(a+b))h(-1))×[NB](a=1.35±0.10)[AA](b=0.89±0.01). The GC/MS analytical method identified nitrosobenzene, azoxybenzene, and azobenzene as NB reduction intermediates, and aniline (AN) as a final product. These experimental results indicate that the alkaline AA reduction of NB to AN mainly proceeds via the direct route, consisting of a series of two-electron or four-electron transfers, and the condensation reaction plays a minor route. Preliminary evaluation of the remediation of spiked NB contaminated soils revealed that maintenance of alkaline pH and a higher water to soil ratio are essential for a successful alkaline AA application.

15.
Water Environ Res ; 87(7): 656-9, 2015 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-26163502

RESUMO

A proposed mechanism for alkaline activation of persulfate involves generation of sulfate (SO(4)(-)), hydroxyl (HO·), and superoxide radicals (O(2)(-)). The present study investigated the feasibility of chloroform (CF) degradation using alkaline activated persulfate and identified the active radical species using a radical inhibition technique. 2-propanol (PrOH) (preferentially reacted with HO·), phenol (preferentially reacted with both HO· and SO(4)(-)), and carbon tetrachloride (CT) (preferentially reacted with O(2)(-)) were used to inhibit the degradation of CF, and the extent of inhibited degradation was used to indicate the predominant radical species. Additions of PrOH and phenol appeared to significantly scavenge SO(4)(-) and HO· and resulted in inhibited CF degradation. Here, the authors demonstrated that SO(4)(-) and HO· were predominant radicals in the alkaline activated persulfate system. The presence of O(2)(-) scavengers (i.e., CT) resulted in a partial inhibition of CF degradation and, hence, one can speculate that O(2)(-) is a minor radical species.


Assuntos
Compostos de Sódio/química , Sulfatos/química , Poluentes Químicos da Água/química , Clorofórmio/química , Sequestradores de Radicais Livres , Concentração de Íons de Hidrogênio , Oxirredução , Purificação da Água
16.
J Contam Hydrol ; 177-178: 158-66, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25941757

RESUMO

Ethylene dichloride tar (EDC-tar) is a dense non-aqueous phase liquid (DNAPL) waste originated from the process of vinyl chloride production, with major constituents including chlorinated aliphatic and aromatic hydrocarbons. This study investigated the feasibility of Surfactant Enhanced Aquifer Remediation (SEAR) for treating EDC-tar contaminated aquifers. Initial experiments explored the potential to enhance the apparent solubility of EDC-tar using single or mixed surfactants. The results showed that an aqueous solution mixed anionic and non-ionic surfactants (i.e., SDS/Tween 80) exhibited higher EDC-tar apparent solubility and lower surface tension than other surfactant systems tested. Additionally, alkaline pH aids in increasing the EDC-tar apparent solubility. In column flushing experiments, it was seen that the alkaline mixed SDS/Tween 80 solution showed better removal of pure EDC-tar from silica sand porous media. Furthermore, separation of EDC-tar in the surfactant solution was conducted employing a salting-out effect. Significant separation of DNAPL was observed when 13 wt.% or more NaCl was added to the solution. Overall, this study evaluates the feasibility of using SEAR for remediating EDC-tar contaminated subsurface soil and groundwater.


Assuntos
Recuperação e Remediação Ambiental/métodos , Dicloretos de Etileno , Tensoativos , Poluentes Químicos da Água , Dicloretos de Etileno/química , Água Subterrânea , Polissorbatos , Poluentes do Solo/química , Solubilidade , Cloreto de Vinil , Poluentes Químicos da Água/química
17.
Chemosphere ; 136: 27-31, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-25912910

RESUMO

Alkaline ascorbic acid (AA) was recently discovered as a novel in-situ chemical reduction (ISCR) reagent for remediating chlorinated solvents in the subsurface. For this ISCR process, the maintenance of an alkaline pH is essential. This study investigated the possibility of the reduction of carbon tetrachloride (CT) using alkaline AA solution buffered by phosphate and by NaOH. The results indicated that CT was reduced by AA, and chloroform (CF) was a major byproduct at a phosphate buffered pH of 12. However, CT was completely reduced by AA in 2M NaOH without CF formation. In the presence of iron/soil minerals, iron could be reduced by AA and Fe(2+) tends to precipitate on the mineral surface to accelerate CT degradation. A simultaneous transfer of hydrogenolysis and dichloroelimination would occur under phosphate buffered pH 12. This implies that a high alkaline environment is a crucial factor for maintaining the dominant pathway of two electron transfer from dianionic AA to dehydroascorbic acid, and to undergo dichloroelimination of CT. Moreover, threonic acid and oxalic acid were identified to be the major AA decomposition products in alkaline solutions.


Assuntos
Ácido Ascórbico/química , Tetracloreto de Carbono/química , Modelos Químicos , Purificação da Água/métodos , Soluções Tampão , Clorofórmio/química , Ferro/química , Minerais , Oxirredução , Solo , Soluções
18.
Chemosphere ; 93(11): 2711-6, 2013 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-24099898

RESUMO

Persulfate anion (S2O8(2-)), a widely used in situ chemical oxidation agent, is increasingly applied for environmental remediation. However, limited information on environmental and toxicological effects is available for the evaluation of the environmental risk of exposure to S2O8(2-), particularly after its application. In this study, the acute toxic effects on the common carp (Cyprinus carpio) were employed as a model to investigate S2O8(2-), sulfate ion (decomposition product of S2O8(2-)), hydrogen/hydroxide ions and also the mixtures of these ion species. Acute toxicity test results showed 96h median lethal concentrations (LC50) of 540±23mgL(-1) for S2O8(2-) and 4100±110mgL(-1) for SO4(2-). S2O8(2-) was considerably more toxic than its decomposition product SO4(2-). Additionally, solution pH was also an important factor influencing toxicity, and S2O8(2-) posed reduced acute toxicity when pH was in the range of 6-10. Water conductivity up to approximately 8000µScm(-1) did not appear to significantly increase fish mortality. In the mixture toxicity test (i.e., S2O8(2-)/OH(-)), LC50 values of 130±10mgL(-1) for S2O8(2-) and 23±2mgL(-1) for OH(-) were lower than those obtained from the individual toxicity tests and therefore exhibited higher toxicity to fish. However, upon complete decomposition of S2O8(2-) in the mixture, a reduction in acute toxicity may be expected. The results of this study revealed that it may be necessary and/or desirable to control the residual S2O8(2-)and pH after S2O8(2-) addition when potential exposure to an aquatic system is a concern.


Assuntos
Sulfatos/toxicidade , Poluentes Químicos da Água/toxicidade , Purificação da Água/métodos , Animais , Carpas , Recuperação e Remediação Ambiental/métodos , Modelos Biológicos , Oxirredução , Sulfatos/análise , Testes de Toxicidade , Poluentes Químicos da Água/análise
19.
Environ Sci Technol ; 47(7): 3299-307, 2013 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-23448585

RESUMO

Ascorbic acid (AA) mediated electron transfer may induce reductive dechlorination of carbon tetrachloride (CCl(4)). This study investigated the role of AA in conjunction with the presence of iron minerals over a wide pH range for the reduction of CCl(4) in aqueous systems. The results indicate that CCl(4) was reduced by AA at a pH of 13 (>pKa(2, AA) of 11.79) and chloroform (CHCl3) was a transformation byproduct of CCl(4). When CCl(4) levels were reduced to near complete disappearance, the decrease of CHCl(3) was then observed. The degradation rate of CCl(4) and also the formation rate of CHCl(3) increased with increased AA concentrations. Analysis of reaction kinetics between CCl(4) and AA revealed an overall second-order reaction with a rate constant of 0.253 ± 0.018 M(-1) s(-1). Furthermore, the reduction rate of CCl(4) by AA at pH of 13 could be enhanced with the presence of iron minerals (Fe(3)O(4), Fe(2)O(3), FeOOH, and FeS2). In the absence or presence of iron minerals, the fraction of CCl(4) transformed to CHCl(3) was less than 1, indicating simultaneous one- and two-electron transfer processes. The end-products of AA at a pH of 13 included threonic acid and oxalic acid. This study highlights the potential of an alkaline AA solution for remediating chlorinated solvents.


Assuntos
Álcalis/química , Ácido Ascórbico/química , Tetracloreto de Carbono/química , Clorofórmio/química , Cromatografia Líquida , Concentração de Íons de Hidrogênio , Ferro/química , Cinética , Espectrometria de Massas , Minerais/química , Solo/química , Soluções
20.
J Hazard Mater ; 231-232: 120-6, 2012 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-22795588

RESUMO

The goal of this study was to produce a reactive granular activated carbon (GAC) coated with pyrite (FeS(2)) for environmental remediation, which would combine both functions of GAC adsorption and FeS(2) reduction reactions. GAC-FeS(2) composite materials have been successfully prepared via sequential processes, i.e., incipient wetness iron impregnation, transformation into hematite (Fe(2)O(3)) by calcination at 300 °C and sulfurization by calcination at 400 °C. The point of zero charge (pH(PZC)) of GAC washed with nitric acid (HNO(3)) decreased to improve the drawing of iron ionic species into the pores of GAC and the results of FTIR confirmed the predominance of carboxylic acid groups which cause a negative charged GAC surface. XRD results indicated that the calcined composites are transitional GAC-Fe(2)O(3) and final GAC-FeS(2). The obtained FeS(2) crystallite size calculated using Scherrer formulae was around 31-34 nm and SEM/SEI showed FeS(2) had an angular shape. The existence of FeS(2) in GAC gave rise to a significant reduction of BET surface and pore volume. However, even though these reductions may result in the decrease of adsorption capacity when compared to the virgin GAC, the coated reactive FeS(2) may result in the abiotic transformation of adsorbates such as trichloroethylene (TCE) and this would compensate for the loss of adsorption. Furthermore, the preliminary results of TCE experiments on GAC-FeS(2) adsorption/dechlorination revealed that the composite initially accumulated and confined TCE on GAC and gradually dechlorinated TCE by embedded FeS(2).


Assuntos
Carvão Vegetal/química , Recuperação e Remediação Ambiental , Ferro/química , Sulfetos/química , Adsorção , Microscopia Eletrônica de Varredura , Espectrometria por Raios X , Tricloroetileno/química , Difração de Raios X
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