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Organocopper complexes during roxarsone degradation in wastewater lagoons

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Abstract

Background, aim, and scope

Organoarsenical-containing animal feeds that promote growth and resistance to parasites are mostly excreted unchanged, ending up in nearby wastewater storage lagoons. Earlier work documented the partial transformation of organoarsenicals, such as, 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) to the more toxic inorganic arsenate [As(V)] and 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA). Unidentified roxarsone metabolites using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC/ICP-MS) were also inferred from the corresponding As mass balance. Earlier batch experiments in our laboratory suggested the presence of organometallic (Cu) complexes during relevant roxarsone degradation experiments. We hypothesized that organocopper compounds were complexed to roxarsone, mediating its degradation in field-collected swine wastewater samples from storage lagoons. The objective of this study was to investigate the role of organometallic (Cu) complexes during roxarsone degradation under aerobic conditions in swine wastewater suspensions, using electrospray ionization mass spectrometry (ES-MS).

Materials and methods

Two swine wastewater samples differing in % solids content and total recoverable Cu concentrations were reacted with 500 ppb of roxarsone under aerobic conditions for 16 days. LC/ICP-MS and ES-MS were used for As speciation analyses, and characterization of metal–organoarsenical complexes in swine wastewater subsamples, respectively.

Results and discussion

An organocopper roxarsone metabolite was found only in the high-Cu wastewater sample, suggesting the role of Cu in roxarsone degradation under aerobic conditions. The organocopper metabolite was not found in the low-Cu wastewater sample, because roxarsone did not undergo degradation under aerobic conditions even after 16 days.

Conclusions

Aerobic degradation of organoarsenicals (roxarsone) has not been documented before. Preliminary dataset from this study illustrates the direct and/or indirect association of particulate Cu in catalyzing roxarsone degradation under aerobic conditions in samples with high % solids content.

Recommendations and perspectives

Concerns regarding the degradation of roxarsone in wastewater to the more toxic inorganic As may be partially linked to the presence of particulate Cu. The presence of Cu in wastewater-suspended particle surfaces has never been coupled before to organoarsenicals degradation reactions, thus, further studies are needed to elucidate the related reaction mechanisms and pathways. Water depth-dependent solid particle distribution profiles in wastewater storage lagoons could provide empirical evidence towards the design of effective degradation practices for nitrophenol-containing compounds, such as, organoarsenical-containing antibiotics, or explosive munitions compounds.

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References

  • Andra SS, Datta R, Sarkar D, Makris KC, Mullens CP, Sahi SV, Bach SBH (2009) Induction of lead-binding phytochelatins in vetiver grass [Vetiveria zizanioides (L.)]. J Environ Qual 38:868–877

    Article  CAS  Google Scholar 

  • Bednar AJ, Garbarino JR, Ferrer I, Rutherford DW, Wershaw RL, Ranville JF, Wildeman TR (2003) Photodegradation of roxarsone in poultry litter leachates. Sci Total Environ 302:237–245

    Article  CAS  Google Scholar 

  • Brown BL, Slaghter AD, Schreiber ME (2005) Controls on roxarsone transport in agricultural watersheds. Appl Geochem 20:123–133

    Article  CAS  Google Scholar 

  • Chapman HD, Johnson ZB (2002) Use of antibiotics and roxarsone in broiler chickens in the USA: analysis for the years 1995 to 2000. Poult Sci 81:356–364

    CAS  Google Scholar 

  • Cortinas I, Field JA, Kopplin M, Garbarino JR, Gandolfi AJ, Sierra-Alvarez R (2006) Anaerobic biotransformation of roxarsone and related N-substituted phenylarsonic acids. Environ Sci Technol 40:2951–2957

    Article  CAS  Google Scholar 

  • Czarnecki GL, Baker DH (1985) Reduction of liver copper concentration by the organic arsenical, 3-nitro-4-hydroxyphenylarsonic acid. J Anim Sci 30:440–450

    Google Scholar 

  • del Castilho P, Chardon WJ, Salomons W (1993) Influence of cattlemanure slurry application on the solubility of cadmium, copper and zinc in a manured acidic loamy-sand soil. J Environ Qual 22:689–697

    Article  Google Scholar 

  • Deo RP, Halden RU (2010) Effect of sample filtration on the quality of monitoring data reported for organic compounds during wastewater treatment. J Environ Monit

  • Grafe M, Eick MJ, Grossl PR (2001) Adsorption of arsenate (V) and arsenite (III) on goethite in the presence and absence of dissolved organic carbon. Soil Sci Soc Am J 65:1680–1687

    CAS  Google Scholar 

  • Grafe M, Eick MJ, Grossl PR, Saunders AM (2002) Adsorption of arsenate and arsenite on ferrihydrite in the presence and absence of dissolved organic carbon. J Environ Qual 31:1115–1123

    CAS  Google Scholar 

  • Jia DA, Zhou DM, Wang YJ, Zhu HW, Chen JL (2008) Adsorption and cosorption of Cu(II) and tetracycline on two soils with different characteristics. Geoderma 146:224–230

    Article  CAS  Google Scholar 

  • Katritzky AR, Shipkova PA, Qi M, Powell DH, Siskin M, Ferrughelli DT, Durst HD (1996) Aqueous high-temperature chemistry of arsenic-containing compounds in water at 300°C. Toxicol Environ Chem 59:239–249

    Google Scholar 

  • Ljung KS, Kippler MJ, Goessler W, Margaretha Grander G, Nermell BM, Vahter ME (2009) Maternal and early life exposure to manganese in rural Bangladesh. Environ Sci Technol 43:2595–2601

    Article  CAS  Google Scholar 

  • Makris KC, Quazi S, Punamiya P, Sarkar D, Datta R (2008a) Fate of arsenic in swine waste from concentrated animal feeding operations. J Environ Qual 37:1626–1633

    Article  CAS  Google Scholar 

  • Makris KC, Salazar JA, Quazi S, Andra SS, Sarkar D, Bach SBH, Datta R (2008b) Controlling the fate of roxarsone and inorganic arsenic in poultry litter. J Environ Qual 37:963–971

    Article  CAS  Google Scholar 

  • Roy P, Saha A (2002) Metabolism and toxicity of arsenic: a human carcinogen. Curr Sci 82:38–45

    CAS  Google Scholar 

  • Rutherford DW, Bednar AJ, Garbarino JR, Needham R, Staver KW, Wershaw RL (2003) Environmental fate of roxarsone in poultry litter. Part II. Mobility of arsenic in soils amended with poultry litter. Environ Sci Technol 37:1515–1520

    Article  CAS  Google Scholar 

  • Sandrin TR, Maier RM (2003) Impact of metals on the biodegradation of organic pollutants. Environ Health Perspect 111:1093–1101

    CAS  Google Scholar 

  • Silbergeld EK, Nachman K (2008) The environmental and public health risks associated with arsenical use in animal feeds. Ann N Y Acad Sci 1140:346–357

    Article  CAS  Google Scholar 

  • Spark KM, Wells JD, Johnson BB (1997) The interaction of a humic acid with heavy metals. Aust J Soil Res 35:89–101

    Article  CAS  Google Scholar 

  • Stolz JF, Perera E, Kilonzo B, Kail B, Crable B, Fisher E, Ranganathan M, Wormer L, Basu P (2007) Biotransformation of 3-nitro-4-hydroxybenzene arsonic acid (roxarsone) and release of inorganic arsenic by Clostridium species. Environ Sci Technol 41:818–823

    Article  CAS  Google Scholar 

  • USEPA (2000) Test methods for evaluationg solid waste, physical/chemical methods, USEPA-65 FR 70678. Draft update 1VB SW-846. U.S.S Gov. Print. Office, Washington, DC

  • Wang YJ, Jia DA, Sun RJ, Zhu HW, Zhou DM (2008) Adsorption and cosorption of tetracycline and copper(II) on montmorillonite as affected by solution pH. Environ Sci Technol 42:3254–3259

    Article  CAS  Google Scholar 

  • Yiannikouris A, Connolly C, Power R, Lobinski R (2009) Characterization of metal–peptide complexes in feed supplements of essential trace elements. Metallomics 1:235–248

    Article  CAS  Google Scholar 

Download references

Acknowledgement

The authors thank the USEPA-STAR program for funding this study and the North Carolina Department of Agriculture and Consumer Services, Agronomic Division, Plant/Waste/Solution Section, Raleigh, NC for sending a portion of swine waste samples used in this study.

Author information

Authors and Affiliations

  1. Environmental Geochemistry Laboratory, University of Texas at San Antonio, San Antonio, TX, USA

    Syam S. Andra

  2. Cyprus International Institute for Environmental and Public Health in association with the Harvard School of Public Health, Cyprus University of Technology, Corner Athinon and Nikou Xiouta, Limassol, 3041, Cyprus

    Konstantinos C. Makris

  3. Department of Soil, Water, and Climate, University of Minnesota, St. Paul, MN, USA

    Shahida Quazi

  4. Department of Earth and Environmental Studies, Montclair State University, Montclair, NJ, USA

    Dibyendu Sarkar

  5. Biological Sciences, Michigan Technological University, Houghton, MI, USA

    Rupali Datta

  6. Department of Chemistry, University of Texas at San Antonio, San Antonio, TX, USA

    Stephan B. H. Bach

Authors
  1. Syam S. Andra
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  2. Konstantinos C. Makris
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  3. Shahida Quazi
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  4. Dibyendu Sarkar
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  5. Rupali Datta
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  6. Stephan B. H. Bach
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Corresponding author

Correspondence to Konstantinos C. Makris.

Additional information

Responsible editor: Philippe Garrigues

Authors S.S.A. and K.C.M. contributed equally to this work as co-first authors.

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Andra, S.S., Makris, K.C., Quazi, S. et al. Organocopper complexes during roxarsone degradation in wastewater lagoons. Environ Sci Pollut Res 17, 1167–1173 (2010). https://doi.org/10.1007/s11356-009-0281-7

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