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Environmental problems - Chemical approaches
RESEARCH FRONT

In situ oxalic acid injection to accelerate arsenic remediation at a superfund site in New Jersey

Karen Wovkulich A B E , Martin Stute B C , Brian J. Mailloux C , Alison R. Keimowitz D , James Ross B , Benjamin Bostick B , Jing Sun A B and Steven N. Chillrud B
+ Author Affiliations
- Author Affiliations

A Department of Earth and Environmental Sciences, Columbia University, New York, NY 10027, USA.

B Lamont-Doherty Earth Observatory, Palisades, NY 10964, USA.

C Department of Environmental Sciences, Barnard College, New York, NY 10027, USA.

D Department of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA.

E Corresponding author. Present address: Department of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA. Email: kawovkulich@vassar.edu

Environmental Chemistry 11(5) 525-537 https://doi.org/10.1071/EN13222
Submitted: 7 December 2013  Accepted: 25 June 2014   Published: 25 September 2014

Environmental context. Arsenic is one of the most common contaminants at US Superfund sites; therefore, establishing techniques to accelerate As remediation could benefit many sites. In a pilot scale study, we determined that addition of oxalic acid to the subsurface has the potential to increase arsenic release from sediments and possibly improve remediation efficiency by pump and treat techniques. Because pump and treat remediation can require many decades to sufficiently decrease contaminant levels, methods for improving remediation could lead to substantial savings in time and resources.

Abstract. Arsenic is a prevalent contaminant at a large number of US Superfund sites; establishing techniques that accelerate As remediation could benefit many sites. Hundreds of tonnes of As were released into the environment by the Vineland Chemical Co. in southern New Jersey during its manufacturing lifetime (1949–1994), resulting in extensive contamination of surface and subsurface soils and sediments, groundwater, and the downstream watershed. Despite substantial intervention at this Superfund site, sufficient aquifer clean up could require many decades if based on traditional pump and treat technologies only. Laboratory column experiments have suggested that oxalic acid addition to contaminated aquifer solids could promote significant As release from the solid phase. To evaluate the potential of chemical additions to increase As release in situ and boost treatment efficiency, a forced gradient pilot scale study was conducted on the Vineland site. During spring and summer 2009, oxalic acid and bromide tracer were injected into a small portion (~50 m2) of the site for 3 months. Groundwater samples indicate that introduction of oxalic acid led to increased As release. Between 2.9 and 3.6 kg of As were removed from the sampled wells as a result of the oxalic acid treatment during the 3-month injection. A comparison of As concentrations on sediment cores collected before and after treatment and analysed using X-ray fluorescence spectroscopy suggested reduction in As concentrations of ~36 % (median difference) to 48 % (mean difference). Although further study is necessary, the addition of oxalic acid shows potential for accelerating treatment of a highly contaminated site and decreasing the As remediation time-scale.


References

[1]  Arsenic Treatment Technologies for Soil, Waste, and Water 2002 (US Environmental Protection Agency: Cincinnati, OH, USA). Available at http://www.clu-in.org/download/remed/542r02004/arsenic_report.pdf [Verified 5 August 2014].

[2]  EPA Basic Query for National Priorities List, Superfund, US EPA 2007 (US Environmental Protection Agency: Cincinnati, OH, USA).

[3]  D. M. Mackay, J. A. Cherry, Groundwater contamination: pump-and-treat remediation. Environ. Sci. Technol. 1989, 23, 630.
Groundwater contamination: pump-and-treat remediation.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1MXktFaitL4%3D&md5=ec92ed836ef9eaa7bf942b5ffb35f333CAS |

[4]  C. D. Palmer, W. Fish, Chemical enhancements to pump-and-treat remediation, in EPA Ground Water Issue, EPA/540/S-92/OOl 1992 (US Environmental Protection Agency, Office of Research and Development, Office of Solid Waste and Emergency Response). Available at http://www.epa.gov/superfund/remedytech/tsp/download/chemen.pdf [Verified 5 August 2014].

[5]  Treatment Technologies for Site Cleanup: Annual Status Report, 12th edn 2007 (US Environmental Protection Agency: Cincinnati, OH, USA). Available at http://www.clu-in.org/download/remed/asr/12/asr12_main_body.pdf [Verified 5 August 2014].

[6]  P. L. Smedley, D. G. Kinniburgh, A review of the source, behaviour and distribution of arsenic in natural waters. Appl. Geochem. 2002, 17, 517.
A review of the source, behaviour and distribution of arsenic in natural waters.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XhvVSmur0%3D&md5=e91f95bcfc6b5336d0e64af1fca2a6c1CAS |

[7]  K. Wovkulich, B. J. Mailloux, A. Lacko, A. R. Keimowitz, M. Stute, H. J. Simpson, S. N. Chillrud, Chemical treatments for mobilizing arsenic from contaminated aquifer solids to accelerate remediation. Appl. Geochem. 2010, 25, 1500.
Chemical treatments for mobilizing arsenic from contaminated aquifer solids to accelerate remediation.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXht1Wjtb%2FJ&md5=9064a83f1ff8b7a170b265c97e73560dCAS | 21076621PubMed |

[8]  K. Wovkulich, B. J. Mailloux, B. C. Bostick, H. Dong, M. E. Bishop, S. N. Chillrud, Use of microfocused X-ray techniques to investigate mobilization of As by oxalic acid. Geochim. Cosmochim. Acta 2012, 91, 254.
Use of microfocused X-ray techniques to investigate mobilization of As by oxalic acid.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtFCjs7zI&md5=a279af92cb8f8e8746705928c21d20bdCAS | 23175572PubMed |

[9]  Pump-and-Treat Ground-Water Remediation: a Guide for Decision Makers and Practitioners. Office of Research and Development, EPA/625/R-95/005 1996 (US Environmental Protection Agency: Cincinnati, OH, USA).

[10]  E. A. Voudrias, Pump-and-treat remediation of groundwater contaminated by hazardous waste: can it really be achieved? Global Nest Int. J. 2001, 3, 1.

[11]  D. Ahmann, L. R. Krumholz, H. F. Hemond, D. R. Lovley, F. M. M. Morel, Microbial mobilization of arsenic from sediments of the Aberjona Watershed. Environ. Sci. Technol. 1997, 31, 2923.
Microbial mobilization of arsenic from sediments of the Aberjona Watershed.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXlsFymtrw%3D&md5=f2bc624c6c0b2099ef9fe8467449af7dCAS |

[12]  H. M. Anawar, J. Akai, H. Sakugawa, Mobilization of arsenic from subsurface sediments by effect of bicarbonate ions in groundwater. Chemosphere 2004, 54, 753.
Mobilization of arsenic from subsurface sediments by effect of bicarbonate ions in groundwater.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXos1Ogu7o%3D&md5=6acf865ef29674af6e6f30dddc99eb4eCAS | 14602108PubMed |

[13]  J. E. Darland, W. P. Inskeep, Effects of pH and phosphate competition on the transport of arsenate. J. Environ. Qual. 1997, 26, 1133.
Effects of pH and phosphate competition on the transport of arsenate.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXlt1ShsrY%3D&md5=8466fe4eacf475266924aff6136cf3b1CAS |

[14]  S. Dixit, J. G. Hering, Comparison of arsenic(V) and arsenic(III) sorption onto iron oxide minerals: implications for arsenic mobility. Environ. Sci. Technol. 2003, 37, 4182.
Comparison of arsenic(V) and arsenic(III) sorption onto iron oxide minerals: implications for arsenic mobility.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXmtFOltr8%3D&md5=e95cefdfa6e7bd583150adbcd471263fCAS | 14524451PubMed |

[15]  J. Youngran, M. H. Fan, J. Van Leeuwen, J. F. Belczyk, Effect of competing solutes on arsenic(V) adsorption using iron and aluminum oxides. J. Environ. Sci. 2007, 19, 910.
Effect of competing solutes on arsenic(V) adsorption using iron and aluminum oxides.Crossref | GoogleScholarGoogle Scholar |

[16]  B. K. Mandal, K. T. Suzuki, Arsenic round the world: a review. Talanta 2002, 58, 201.
Arsenic round the world: a review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XlvVGnsbg%3D&md5=af84d99c9b1453ef9681eac40e82a044CAS | 18968746PubMed |

[17]  T. R. Fox, N. B. Comerford, Low-molecular-weight organic-acids in selected forest soils of the southeastern USA. Soil Sci. Soc. Am. J. 1990, 54, 1139.
Low-molecular-weight organic-acids in selected forest soils of the southeastern USA.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXktFGitQ%3D%3D&md5=d48aa23a406f65ea94624a2b89c9073aCAS |

[18]  B. W. Strobel, Influence of vegetation on low-molecular-weight carboxylic acids in soil solution – a review. Geoderma 2001, 99, 169.
Influence of vegetation on low-molecular-weight carboxylic acids in soil solution – a review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXkslGnsQ%3D%3D&md5=22e0fe035507d5d12134c84f6a31a681CAS |

[19]  P. A. W. van Hees, U. S. Lundstrom, R. Giesler, Low molecular weight organic acids and their Al-complexes in soil solution – composition, distribution and seasonal variation in three podzolized soils. Geoderma 2000, 94, 173.
Low molecular weight organic acids and their Al-complexes in soil solution – composition, distribution and seasonal variation in three podzolized soils.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXhtFyis70%3D&md5=9e7e7e498dd68338b8c758ce5a706d24CAS |

[20]  D. L. Jones, Organic acids in the rhizosphere – a critical review. Plant Soil 1998, 205, 25.
Organic acids in the rhizosphere – a critical review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXhtlGjs78%3D&md5=c4c36a5b71f655c2908e55f121734685CAS |

[21]  R. Shi, Y. F. Jia, C. Wang, Y. Shuhua, Mechanism of arsenate mobilization from goethite by aliphatic carboxylic acid. J. Hazard. Mater. 2009, 163, 1129.
Mechanism of arsenate mobilization from goethite by aliphatic carboxylic acid.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhvFais7o%3D&md5=1a9ab9f05e8c0bb0a161bb9c5d14bf19CAS | 18752889PubMed |

[22]  S. Z. Zhang, W. Li, X. Q. Shan, A. X. Lu, P. J. Zhou, Effects of low molecular weight organic anions on the release of arsenite and arsenate from a contaminated soil. Water Air Soil Pollut. 2005, 167, 111.
Effects of low molecular weight organic anions on the release of arsenite and arsenate from a contaminated soil.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXhtFartLjN&md5=538a664d7d5e5b18bc0e7eb93d36eeb6CAS |

[23]  L. Luo, S. Zhang, X.-Q. Shan, Y.-G. Zhu, Effects of oxalate and humic acid on arsenate sorption by and desorption from a Chinese red soil. Water Air Soil Pollut. 2006, 176, 269.
Effects of oxalate and humic acid on arsenate sorption by and desorption from a Chinese red soil.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XptVGrurw%3D&md5=bef1af9e68075a2db12499c4f69c3031CAS |

[24]  N. E. Keon, C. H. Swartz, D. J. Brabander, C. Harvey, H. F. Hemond, Validation of an arsenic sequential extraction method for evaluating mobility in sediments. Environ. Sci. Technol. 2001, 35, 2778.
Validation of an arsenic sequential extraction method for evaluating mobility in sediments.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXjvFSqu7s%3D&md5=491ed2069a22d7f6bf670fe52a777f48CAS | 11452609PubMed |

[25]  C. H. Swartz, N. K. Blute, B. Badruzzman, A. Ali, D. Brabander, J. Jay, J. Besancon, S. Islam, H. F. Hemond, C. F. Harvey, Mobility of arsenic in a Bangladesh aquifer: inferences from geochemical profiles, leaching data, and mineralogical characterization. Geochim. Cosmochim. Acta 2004, 68, 4539.
Mobility of arsenic in a Bangladesh aquifer: inferences from geochemical profiles, leaching data, and mineralogical characterization.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXptlylsrw%3D&md5=f1a427a86c89e651da5865219f7e1f8aCAS |

[26]  W. W. Wenzel, N. Kirchbaumer, T. Prohaska, G. Stingeder, E. Lombi, D. C. Adriano, Arsenic fractionation in soils using an improved sequential extraction procedure. Anal. Chim. Acta 2001, 436, 309.
Arsenic fractionation in soils using an improved sequential extraction procedure.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXktVGnt7c%3D&md5=3fc82fd197865c6a5648b5571db01a87CAS |

[27]  A. J. Slowey, S. B. Johnson, M. Newville, G. E. Brown, Speciation and colloid transport of arsenic from mine tailings. Appl. Geochem. 2007, 22, 1884.
Speciation and colloid transport of arsenic from mine tailings.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXpsFWqtro%3D&md5=588a8bc70912caa11c59efb0c2339559CAS |

[28]  D. G. Klarup, The influence of oxalic acid on release rates of metals from contaminated river sediment. Sci. Total Environ. 1997, 204, 223.
The influence of oxalic acid on release rates of metals from contaminated river sediment.Crossref | GoogleScholarGoogle Scholar |

[29]  D. Mohapatra, P. Singh, W. Zhang, P. Pullammanappallil, The effect of citrate, oxalate, acetate, silicate, and phosphate on stability of synthetic arsenic-loaded ferrihydrite and Al-ferrihydrite. J. Hazard. Mater. 2005, 124, 95.
The effect of citrate, oxalate, acetate, silicate, and phosphate on stability of synthetic arsenic-loaded ferrihydrite and Al-ferrihydrite.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXmvFGjt7o%3D&md5=157fa5f0bc78f0fe536714ff36c567b7CAS | 15961223PubMed |

[30]  Vineland Chemical Company Site Final Draft, Feasibility Study Report, River Areas, Vineland NJ. 1989 (US Environmental Protection Agency: Vineland, NJ).

[31]  Vineland Chemical Co., Inc., National Priority List site fact sheet 2006 (US Environmental Protection Agency). Available at http://www.epa.gov/Region2/superfund/npl/0200209c.pdf [Verified 5 August 2014].

[32]  Technical Fact Sheet: Final Rule for Arsenic in Drinking Water, EPA 815-F-00-016 2001 (US Environmental Protection Agency: N. J. Vineland, ). Available at http://water.epa.gov/lawsregs/rulesregs/sdwa/arsenic/regulations_techfactsheet.cfm [Verified 5 August 2014].

[33]  A. R. Keimowitz, Y. Zheng, S. N. Chillrud, B. Mailloux, H. B. Jung, M. Stute, H. J. Simpson, Arsenic redistribution between sediments and water near a highly contaminated source. Environ. Sci. Technol. 2005, 39, 8606.
Arsenic redistribution between sediments and water near a highly contaminated source.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXhtVyqsrzI&md5=ef4c11d1b7070fce52c3f194ded0a4c1CAS | 16329197PubMed |

[34]  G. Pump, T. Systems, Summary of Selected Cost and Performance Information at Superfund-Financed Sites, EPA 542-R-01-021a 2001 (US Environmental Protection Agency: Cincinnati, OH, USA). Available at http://www.epa.gov/superfund/cleanup/postconstruction/p1report.pdf [Verified 6 August 2014].

[35]  Classification Exception Area and Well Restriction Area Report. Vineland Chemical Company Superfund Site, Vineland, NJ, Prepared for USEPA, Region II 2007 (US Army Core of Engineers: Philadelphia, PA, USA).

[36]  K. Wovkulich, Laboratory and Field Studies Directed Toward Accelerating Remediaton at a Major US Superfund Site in New Jersey 2011, PhD thesis, Columbia University, New York.

[37]  K. Wovkulich, M. Stute, T. J. Protus, B. J. Mailloux, S. N. Chillrud, Injection system for a multiwell injection using a single pump. Ground Water Monit. Remediat. 2011, 31, 79.
Injection system for a multiwell injection using a single pump.Crossref | GoogleScholarGoogle Scholar |

[38]  M. Q. Fleisher, R. Anderson, Particulate matter digestion (from MG to 10’s of G) and radionuclide blanks, in Marine Particles: Analysis and Characterization (Eds D. C. Hurd, D. W. Spencer) 1991, vol. 63, pp. 221–222 (American Geophysical Union: Washington, DC).

[39]  Right to Know, Hazardous Substance Fact Sheet, Oxalic Acid 2010 (NJ Department of Health and Senior Services: N. J. Trenton, USA). Available at http://nj.gov/health/eoh/rtkweb/documents/fs/1445.pdf [Verified 5 August 2014].

[40]  A. Baghel, B. Singh, P. Pandey, K. Sekhar, A rapid field detection method for arsenic in drinking water. Anal. Sci. 2007, 23, 135.
A rapid field detection method for arsenic in drinking water.Crossref | GoogleScholarGoogle Scholar | 17297222PubMed |

[41]  Toxicological Profile for Arsenic 2007 (US Department of Health and Human Services, Agency for Toxic Substances and Disease Registry: G. A. Atlanta, USA). Available at http://www.atsdr.cdc.gov/toxprofiles/tp2.pdf [Verified 5 August 2014].

[42]  N. Sahin, Oxalotrophic bacteria. Res. Microbiol. 2003, 154, 399.
Oxalotrophic bacteria.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXlvVWjt7Y%3D&md5=b6c0c7f4de137efbfbf5ed63f7ce7636CAS | 12892846PubMed |

[43]  D. Panias, M. Taxiarchou, I. Paspaliaris, A. Kontopoulos, Mechanisms of dissolution of iron oxides in aqueous oxalic acid solutions. Hydrometallurgy 1996, 42, 257.
Mechanisms of dissolution of iron oxides in aqueous oxalic acid solutions.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28XksF2nsLk%3D&md5=ac5b0a92611b516aaaee278348f97758CAS |

[44]  S. O. Lee, T. Tran, B. H. Jung, S. J. Kim, M. J. Kim, Dissolution of iron oxide using oxalic acid. Hydrometallurgy 2007, 87, 91.
Dissolution of iron oxide using oxalic acid.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXmvVelu7c%3D&md5=9a724696fd534ad0621919a9fbb45fa3CAS |

[45]  Y. Q. Tao, S. Z. Zhang, W. Jian, C. G. Yuan, X. Q. Shan, Effects of oxalate and phosphate on the release of arsenic from contaminated soils and arsenic accumulation in wheat. Chemosphere 2006, 65, 1281.
Effects of oxalate and phosphate on the release of arsenic from contaminated soils and arsenic accumulation in wheat.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XhtVagsbzO&md5=0ac2b145170fddbd7f09cef0171eb43cCAS |

[46]  Z. Hongshao, R. Stanforth, Competitve adsorption of phosphate and arsenate on goethite. Environ. Sci. Technol. 2001, 35, 4753.
Competitve adsorption of phosphate and arsenate on goethite.Crossref | GoogleScholarGoogle Scholar | 1:STN:280:DC%2BD38%2Fksl2jtQ%3D%3D&md5=73b27143fb938d5777bd58f2518af6eaCAS | 11775149PubMed |

[47]  A. Jain, R. H. Loeppert, Effect of competing anions on the adsorption of arsenate and arsenite by ferrihydrite. J. Environ. Qual. 2000, 29, 1422.
Effect of competing anions on the adsorption of arsenate and arsenite by ferrihydrite.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmvFKiur4%3D&md5=1adef39dcd84ee8f6948b0ffc20c42bcCAS |

[48]  Y. F. Jia, L. Y. Xu, Z. Fang, G. P. Demopoulos, Observation of surface precipitation of arsenate on ferrihydrite. Environ. Sci. Technol. 2006, 40, 3248.
Observation of surface precipitation of arsenate on ferrihydrite.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XjtlOisL0%3D&md5=b4fd541906e5e2eef1c28298362122e6CAS |

[49]  Draft Report of Hydrogeologic Investigations/Capture Zone Analysis, the Vineland Chemical Superfund Site, Vineland, NJ 2003 (Skelly and Loy, Inc. Engineers-Consultants: Harrisburg, PA, USA).

[50]  S. E. Spayd, S. W. Johnson, Guidelines for Delineation of Well Head Protection Areas in New Jersey. New Jersey Geological Survey, Open File Report OFR 03-1 2003 (Trenton, NJ, USA). Available at http://www.state.nj.us/dep/njgs/whpaguide.pdf [Verified 5 August 2014].

[51]  E. O. Holzbecher, Modeling Density-Driven Flow in Porous Media: Principles, Numerics, Software 1998 (Springer: New York).