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Optimized extraction of inorganic arsenic species from a foliose lichen biomonitor

  • Eve M. Kroukamp
  • Taddese W. Godeto
  • Patricia B. C. ForbesEmail author
Research Article
  • 80 Downloads

Abstract

To assess the two most toxicologically relevant species of As, namely arsenite (As(III)) and arsenate (As(V)), chromatographic separations often require two separate chromatographic columns to address the co-elution of arsenobetaine (AsB) with As(III). This issue is typically observed using conventional isocratic methods on anion exchange columns, increasing cost and analysis time. Here, we optimize the extraction of inorganic As from a lichen air biomonitor and develop an isocratic method for the chromatographic separation of five common As species on a PRP X-100 anion exchange column, resulting in the complete baseline separation of all species under study. This method was then applied to lichen biomonitors from an urban and rural site to demonstrate its use. In order of abundance, the various arsenic species in lichens from the urban site in South Africa were As(V) > As(III) > AsB > dimethylarsinic acid (DMA) > monomethylarsonic acid (MMA), and As(V) > AsB > As(III) > DMA > MMA for the rural site, where MMA was present in extremely low, non-quantifiable concentrations in lichens from both sites. Total concentrations of As were higher in samples from the urban site (6.43 ± 0.25 μg/g) than in those from the rural site (1.87 ± 0.05 μg/g), with an overall extraction efficiency of 19% and 40%, respectively. The optimized method utilized relatively inexpensive solvents and is therefore low-cost and eco-friendly in comparison with conventional chromatographic techniques. This is the first study which addresses the optimized extraction and characterization of As species in a South African lichen biomonitor of air pollution.

Graphical abstract

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Keywords

Arsenic speciation HPLC-ICP-MS Extraction Biomonitor Air pollution Lichen 

Notes

Acknowledgments

The authors would like to thank Johannesburg City Parks and Zoo and the Burri family for allowing sampling to take place on their premises. Special thanks are also given to the following people from PerkinElmer Inc. for their support of this study: Dr. Kenneth Neubauer for his guidance on HPLC-ICP-MS methods; Dr. Mark Upton for training; and Lisa Koorts, Chris de Jager, and Dr.Fadi Abou-Shakra for arranging a loan instrument. Further thanks are given to Rufaro Bhero for his assistance in the preparation of the organic arsenic stock solutions.

Funding information

The financial assistance of the University of Pretoria, University of Johannesburg, and the Department of Higher Education and Training towards this research is hereby acknowledged.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Disclaimer

The opinions expressed and conclusions arrived at are those of the authors and are not necessarily to be attributed to these Universities.

Supplementary material

11356_2019_6073_MOESM1_ESM.docx (5.7 mb)
ESM 1 (DOCX 5797 kb)

References

  1. Alava P, Tack F, Du Laing G, Van de Wiele T (2012) HPLC-ICP-MS method development to monitor arsenic speciation changes by human gut microbiota. Biomed Chromatogr 26:524–533.  https://doi.org/10.1002/bmc.1700 CrossRefGoogle Scholar
  2. Amaral CDB, Nóbrega JA, Nogueira ARA (2014) Investigation of arsenic species stability by HPLC-ICP-MS in plants stored under different conditions for 12 months. Microchem J 117:122–126.  https://doi.org/10.1016/j.microc.2014.06.018 CrossRefGoogle Scholar
  3. Bentley R, Chasteen TG (2002) Microbial methylation of metalloids: arsenic, antimony, and bismuth. Microbiol Mol Biol Rev 66:250–271.  https://doi.org/10.1128/MMBR.66.2.250-271.2002 CrossRefGoogle Scholar
  4. Bergqvist C, Herbert R, Persson I, Greger M (2014) Plants influence on arsenic availability and speciation in the rhizosphere, roots and shoots of three different vegetables. Environ Pollut 184:540–546.  https://doi.org/10.1016/j.envpol.2013.10.003 CrossRefGoogle Scholar
  5. Bissen M, Frimmel FH (2000) Speciation of As (III), As (V), MMA and DMA in contaminated soil extracts by HPLC-ICP-MS. Fresenius J Anal Chem 367:51–55.  https://doi.org/10.1007/s002160051597 CrossRefGoogle Scholar
  6. Blasco M, Domeño C, Nerin C (2006) Use of lichens as pollution biomonitors in remote areas: comparison of PAHs extracted from lichens and atmospheric particles sampled in and around the Somport Tunnel ( Pyrenees ). Environ Sci Technol 40:6384–6391.  https://doi.org/10.1021/es0601484 CrossRefGoogle Scholar
  7. Chakraborti D, Rahman MM, Murrill M, Das R, Siddayya S, Patil S et al (2013) Environmental arsenic contamination and its health effects in a historic gold mining area of the Mangalur greenstone belt of northeastern Karnataka, India. J Hazard Mater 262:1048–1055.  https://doi.org/10.1016/j.jhazmat.2012.10.002 CrossRefGoogle Scholar
  8. Challenger F (1945) Biological methylation. Chem Rev 36:315–361.  https://doi.org/10.1021/cr60115a003 CrossRefGoogle Scholar
  9. Chung J-Y, Yu S-D, Hong Y-S (2014) Environmental source of arsenic exposure. J Prev Med Public Health 47:253–257.  https://doi.org/10.3961/jpmph.14.036 CrossRefGoogle Scholar
  10. Crecelius EA, Johnson CJ, Hofer GC (1974) Contamination of soils near a copper smelter by arsenic, antimony and lead. Water Air Soil Pollut 3:337–342.  https://doi.org/10.1007/BF00226464 Google Scholar
  11. Cullen WR (2014) Chemical mechanism of arsenic biomethylation. Chem Res Toxicol 27:457–461.  https://doi.org/10.1021/tx400441h CrossRefGoogle Scholar
  12. Cullen WR, Reimer KJ (1989) Arsenic speciation in the environment. Chem Rev 89:713–764.  https://doi.org/10.1021/cr00094a002 CrossRefGoogle Scholar
  13. Dembitsky VM, Rezanka T (2003) Natural occurance of arseno compounds in plants, lichens, fungi, algal species, and microorganisms. Plant Sci 165:1177–1192.  https://doi.org/10.1016/j.plantsci.2003.08.007 CrossRefGoogle Scholar
  14. Farinha MM, Šlejkovec Z, van Elteren JT, Wolterbeek HT, Freitas MC (2004) Arsenic speciation in lichens and in coarse and fine airborne particulate matter by HPLC – UV – HG – AFS. J Atmos Chem 49:343–353.  https://doi.org/10.1007/s10874-004-1248-1 CrossRefGoogle Scholar
  15. Farinha MM, Freitas MC, Šlejkovec Z, Wolterbeek HT (2009) Arsenic speciation in Portuguese in situ lichen samples. Appl Radiat Isot 67:2123–2127.  https://doi.org/10.1016/j.apradiso.2009.04.018 CrossRefGoogle Scholar
  16. Forbes PBC, van der Wat L, Kroukamp EM (2015) Chapter 3: Biomonitors, in Comprehensive Analytical Chemistry vol. 70: Monitoring of Air Pollutants: Sampling, Sample Preparation and Analytical Techniques, Patricia Forbes (ed). 53-108, Elsevier, Netherlands.  https://doi.org/10.1016/bs.coac.2015.09.003
  17. Frati L, Brunialti G, Loppi S (2005) Problems related to lichen transplants to monitor trace element deposition in repeated surveys: a case study from central Italy. J Atmos Chem 52:221–230.  https://doi.org/10.1007/s10874-005-3483-5 CrossRefGoogle Scholar
  18. Garelick H, Dybowska A, Valsami-Jones E, Priest ND (2005) Remediation technologies for arsenic contaminated drinking waters. J Soils Sediments 5:182–190.  https://doi.org/10.1065/jss2005.06.140 CrossRefGoogle Scholar
  19. Goodarzi F, Huggins FE (2005) Speciation of arsenic in feed coals and their ash byproducts from canadian power plants burning sub-bituminous and bituminous coals. Energy Fuel 19:905–915.  https://doi.org/10.1021/ef049738i CrossRefGoogle Scholar
  20. Huang JH, Hu KN, Decker B (2011) Organic arsenic in the soil environment: speciation, occurrence, transformation, and adsorption behaviour. Water Air Soil Pollut 219:401–415.  https://doi.org/10.1007/s11270-010-0716-2 CrossRefGoogle Scholar
  21. Johnson DL, Braman RS (1975) Alkyl- and inorganic arsenic in air samples. Chemosphere 6:333–338.  https://doi.org/10.1016/0045-6535(75)90027-2 CrossRefGoogle Scholar
  22. Kazi TG, Jalbani N, Arain MB, Jamali MK, Afridi HI, Shah AQ (2009) Determination of toxic elements in different brands of cigarette by atomic absorption spectrometry using ultrasonic assisted acid digestion. Environ Monit Assess 154:155–167.  https://doi.org/10.1007/s10661-008-0386-3 CrossRefGoogle Scholar
  23. Keith LH (1996) Compilations of EPA’s sampling and analysis methods, 2nd edn. CRC Press, FloridaGoogle Scholar
  24. Koch I, Feldmann J, Wang L, Andrewes P, Reimer KJ, Cullen WR (1999) Arsenic in the Meager Creek hot springs environment, British Columbia, Canada. Sci Total Environ 236:101–117.  https://doi.org/10.1016/S0048-9697(99)00273-9 CrossRefGoogle Scholar
  25. Kroukamp EM, Wondimu TW, Forbes PBC (2016) Metal and metalloid speciation in plants: overview, instrumentation, approaches and commonly assessed elements. Trends Anal Chem 77:87–99.  https://doi.org/10.1016/j.trac.2015.10.007 CrossRefGoogle Scholar
  26. Kroukamp EM, Godeto TW, Forbes PBC (2017) Comparison of sample preparation procedures on metal(loid) fractionation patterns in lichens. Environ Monit Assess 189:451.  https://doi.org/10.1007/s10661-017-6155-4 CrossRefGoogle Scholar
  27. Kuehnelt D, Lintschinger J, Goessler W (2000) Arsenic compounds in terrestrial organisms. IV. Green plants and lichens from an old arsenic smelter site in Austria. Appl Organomet Chem 14:411–420.  https://doi.org/10.1002/1099-0739(200008)14:8%3C411::AID-AOC24%3E3.0.CO;2-M CrossRefGoogle Scholar
  28. Machado A, Šlejkovec Z, van Elteren JT, Freitas MC, Baptista MS (2006) Arsenic speciation in transplanted lichens and tree bark in the framework of a biomonitoring scenario. J Atmos Chem 53:237–249.  https://doi.org/10.1007/s10874-006-9013-2 CrossRefGoogle Scholar
  29. Magalhães MCF (2002) Arsenic. An environmental problem limited by solubility. Pure Appl Chem 74:1843–1850.  https://doi.org/10.1351/pac200274101843 CrossRefGoogle Scholar
  30. Milestone (2014) Milestone application note HPR-FO-55, Lichen, Rev 05_11. www.milestonesrl.com. Accessed 30 February 2017
  31. Monaci F, Fantozzi F, Figueroa R, Parra O, Bargagli R (2012) Baseline element composition of foliose and fruticose lichens along the steep climatic gradient of SW Patagonia (Aisén Region, Chile). J Environ Monit 14:2309–2316.  https://doi.org/10.1039/c2em30246b CrossRefGoogle Scholar
  32. Mrak T, Šlejkovec Z, Jeran Z (2006) Extraction of arsenic compounds from lichens. Talanta 69:251–258.  https://doi.org/10.1016/j.talanta.2005.10.011 CrossRefGoogle Scholar
  33. Mrak T, Simčič J, Pelicon P, Jeran Z, Reis MA, Pinheiro T (2007) Use of micro-PIXE in the study of arsenate uptake in lichens and its influence on element distribution and concentrations. Nucl Instrum Methods Phys Res Sect B 260:245–253.  https://doi.org/10.1016/j.nimb.2007.02.029 CrossRefGoogle Scholar
  34. Mrak T, Šlejkovec Z, Jeran Z, Jaćimović R, Kastelec D (2008) Uptake and biotransformation of arsenate in the lichen Hypogymnia physodes (L.) Nyl. Environ Pollut 151:300–307.  https://doi.org/10.1016/j.envpol.2007.06.011 CrossRefGoogle Scholar
  35. Nearing MM, Koch I, Reimer KJ (2014a) Arsenic speciation in edible mushrooms. Environ Sci Technol 48:14203–14210.  https://doi.org/10.1021/es5038468 CrossRefGoogle Scholar
  36. Nearing MM, Koch I, Reimer KJ (2014b) Complementary arsenic speciation methods: a review. Spectrochim Acta B At Spectrosc 99:150–162.  https://doi.org/10.1016/j.sab.2014.07.001 CrossRefGoogle Scholar
  37. Pisani T, Munzi S, Paoli L, Bačkor M, Loppi S (2011) Physiological effects of arsenic in the lichen Xanthoria parietina (L.) Th. Fr. Chemosphere 82:963–969.  https://doi.org/10.1016/j.chemosphere.2010.10.079 CrossRefGoogle Scholar
  38. Quaghebeur M, Rengel Z (2005) Arsenic speciation governs arsenic uptake and transport in terrestrial plants. Microchim Acta 151:141–152.  https://doi.org/10.1007/s00604-005-0394-8 CrossRefGoogle Scholar
  39. Quaghebeur M, Rengel Z, Smirk M (2003) Arsenic speciation in terrestrial plant material using microwave-assisted extraction, ion chromatography and inductively coupled plasma mass spectrometry. J Anal At Spectrom 18:128–134.  https://doi.org/10.1039/b210744a CrossRefGoogle Scholar
  40. Shah P, Strezov V, Stevanov C, Nelson PF (2007) Speciation of arsenic and selenium in coal combustion products. Energy Fuel 21:506–512.  https://doi.org/10.1021/ef0604083 CrossRefGoogle Scholar
  41. Tanner SD, Baranov VI, Bandura DR (2002) Reaction cells and collision cells for ICP-MS: a tutorial review. Spectrochim Acta B At Spectrosc 57:1361–1452.  https://doi.org/10.1016/S0584-8547(02)00069-1 CrossRefGoogle Scholar
  42. USEPA (1998) Locating and estimating air emissions from sources of arsenic and arsenic compounds, EPA-454/R-98-013. North Carolina. Available from: https://www3.epa.gov/ttnchie1/le/arsenic.pdf
  43. Villaescusa I, Bollinger J-C (2008) Arsenic in drinking water: sources, occurrence and health effects (a review). Rev Environ Sci Biotechnol 7:307–323.  https://doi.org/10.1007/s11157-008-9138-7 CrossRefGoogle Scholar
  44. Watts MJ, Button M, Brewer TS, Jenkin GRT, Harrington CF (2008) Quantitative arsenic speciation in two species of earthworms from a former mine site. J Environ Monit 10:753–759.  https://doi.org/10.1039/b800567b CrossRefGoogle Scholar
  45. Zhang W, Cai Y, Tu C, Ma LQ (2002) Arsenic speciation and distribution in an arsenic hyperaccumulating plant. Sci Total Environ 300:167–177.  https://doi.org/10.1016/S0048-9697(02)00165-1 CrossRefGoogle Scholar
  46. Zhao D, Li HB, Xu JY, Luo J, Ma LQ (2015) Arsenic extraction and speciation in plants: method comparison and development. Sci Total Environ 523:138–145.  https://doi.org/10.1016/j.scitotenv.2015.03.051 CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of Natural and Agricultural SciencesUniversity of PretoriaPretoriaSouth Africa
  2. 2.Spectrum Central Analytical Facility, Faculty of ScienceUniversity of JohannesburgJohannesburgSouth Africa
  3. 3.Department of Chemistry, Faculty of ScienceUniversity of JohannesburgJohannesburgSouth Africa
  4. 4.Laboratory Services BranchOntario Ministry of the Environment, Conservation and ParksTorontoCanada

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