Kiral kirleticiler ve çevresel önemi

Abstract

Kiralite, canlı sistemlerden doğal ve sentetik organik maddelere kadar hayatımızın birçok alanında bulunmaktadır. En genel ifadeyle ayna görüntüsü kendisiyle çakışmayan maddeler olarak tanımlanan kiral moleküller, başta ilaç sanayi ve tıp olmak üzere birçok alanda kullanılmaktadır. Söz konusu maddelere ait ayna görüntülerinden her biri enantiyomer olarak adlandırılır ve kiral maddelere ait enantiyomerlerden biri kullanım amacına uygun hareket ederken diğeri veya her ikisi de çevresel ortamlarda kirliliğe ve canlılarda toksik etkiye neden olabilmektedir. Enantiyomerlerin yalnızca biyolojik değişime uğrama potansiyelleri farklılık göstermekte, bu özelliği sebebiyle kiral kirleticiler, güncel kirliliğin değerlendirilmesi amacıyla çevresel kirlilik araştırmalarına konu olmaktadır. Toprak, sediman, hava ve su ortamının yanı sıra canlılarda da, başta kromatografik yöntemler olmak üzere çeşitli metotlarla tespit edilebilmektedir. Bu derlemede, kiralite ve çevresel açıdan önem arz eden kiral bileşiklerin özellikleri, analiz yöntemleri ve çevredeki akıbetleri değerlendirilmiştir. Çeşitli avantajları nedeniyle endüstriyel uygulamalarda geniş yer bulan kiral bileşiklerden kullanım amacının dışında çevreye salınan bileşikler, biyolojik aktiviteleri nedeniyle çevresel izleme çalışmalarında önem arz etmektedir. Ülkemizde çevresel ortamlarda henüz araştırmalara konu olmaya başlayan kiral kirleticilerin akıbetinin değerlendirilmesi açısından enantiyoseçici davranışlarının anlaşılması önem arz etmektedir.

Keywords

• Enantiyomer,Farmasötik,Kalıcı organik kirleticiler,Kromatografi,Pestisit,Rasemik

Chiral pollutants and their significance in the environment

Abstract

Chirality exists in a wide range of objects in the universe from living creatures to natural or synthetic organic materials. As a common expression, any objects that are not superimposable on its mirror image are described as chiral molecules, and such materials are used in various fields including pharmaceutical industry and medicine. Each mirror image of chiral molecules are called enantiomer and while one of the enantiomers may be active and more toxic than the other in its application area and once they enter to the environmental compartments less-active enantiomer or both enantiomers can cause environmental pollution and toxicity on living organisms. Enantiomers show difference in biological degradation such that this property is used as a useful tool in environmental pollution assessment/research studies. In addition to the environmental compartments such as soil, sediment, air and water, they are also analyzed in living organisms by various methods including primarily the chromatographic methods. In this review, chirality and the properties, analysis methods and fate of the chiral chemicals which have significance in the environmental studies are presented. Due to various advantages, chiral chemicals are used in several industrial products and once they are released to the environment, they become environmentally concerned pollutants and play an important role in environmental monitoring studies due to their biological activities. In our country, although it is very limited, chiral pollutants have already became subject to monitoring studies, hence, understanding the enantioselective degradation of such chemicals in different environmental compartments is important to assess the fate of these chemicals.

Keywords

• Chromatography,Enantiomer,Persistent organic pollutants,Pesticide,Pharmaceutical,Racemic

References

1. Ali I, Aboul-Enein HY. Chiral Pollutants: Distribution, Toxicity and Analysis by Chromatography and Capillary Electrophoresis. Chichester, England, Wiley, 2004.
2. Müller TA, Kohler HPE. "Chirality of pollutants-effects on metabolism and fate". Applied Microbiology and Biotechnology, 64(3), 300-316, 2004.
3. Ali I, Gupta VK, Aboul-Enein HY. "Chirality: A challenge for the environmental scientists". Current Science, 84(2), 152-156, 2003.
4. Wiberg K. Enantiospecific Analysis and Environmental Behavior of Chiral Persistent Organic Pollutants (POPs). PhD Thesis, Umea University, Umea, Sweden, 2002.
5. Kallenborn R, Hühnerfuss H. Chiral Environmental Pollutants: Trace Analysis and Ecotoxicology, Berlin, Deutschland, Springer, 2001.
6. Ulrich EM, Morrison CN, Goldsmith MR, Foreman WT. "Chiral Pesticides: Identification, Description, and Environmental Implications". Reviews of Environmental Contamination and Toxicology, 217, 1-74, 2012.
7. Mislow KM. Introduction to Stereochemistry. 1st ed. Mineola, ABD, Courier Dover Publications, 1965.
8. Eliel EL, Wilen SH. Stereochemistry of Organic Compounds. 1st ed. USA, Wiley-Intersscience, 1994.

9. Venier M, Hites RA. "Chiral organochlorine pesticides in the atmosphere". Atmospheric Environment, 41(4), 768-775, 2007.
10. Wong CS, Hoestra PF, Karlsson H, Backus SM, Mabury SA, Muir DCG. "Enantiomer fractions of chiral organochlorine pesticides and polychlorinated biphenyls in standard and certified reference materials". Chemosphere, 49(10), 1339-1347, 2002.
11. Xie J, Duan Y, Che S. "Chirality of metal nanoparticles in chiral mesoporous silica". Advanced Functional Materials, 22(18), 3784-3792, 2012.
12. Fan Z, Govorov AO. "Plasmonic circular dichroism of chiral metal nanoparticle assemblies". Nano Letters, 10(7), 2580-2587, 2010.
13. Eljarrat E, Guerra P, Barcelo D. "Enantiomeric determination of chiral persistent organic pollutants and their metabolites". Trends in Analytical Chemistry, 27(10), 847-861, 2008.
14. Zipper C, Bolliger C, Fleischmann T, Suter MJF, Angst W, Müller MD, Kohler HPE. "Fate of the herbicides mecoprop, dichlorprop and 2, 4-D in aerobic and anaerobic sewage sludge as determined by laboratory batch studies and enantiomer-specific analysis". Biodegradation, 10(4), 271-278, 1999.
15. Nejem RM. Enantioselective Sensors and Biosensors for Clinical Analysis. PhD Thesis, University of Pretoria, Pretoria, South Africa, 2004.
16. Nguyen LA, He H, Pham-Huy C. "Chiral drugs: An overview". International Journal of Biomedical Science, 2(2), 85-100, 2006.
17. Evans SE, Kasprzyk-Hordern B. "Applications of chiral chromatography coupled with mass spectrometry in the analysis of chiral pharmaceuticals in the environment". Trends in Environmental Analytical Chemistry, 1, 34-51, 2014.
18. Kasprzyk-Hordern B. "Pharmacologically active compounds in the environment and their chirality". Chemical Society Reviews, 39(11), 4466-4503, 2010.
19. Ong AL, Kamaruddin AH, Bhatia S, Long WS, Lim ST, Kumari R. "Performance of free candida antarctica lipase b in the enantioselective esterification of (R)-ketoprofen". Enzyme and Microbial Technology, 39(4), 924-929, 2006.
20. Sheldon RA. "Chirotechnology: Designing economic chiral syntheses". Journal of Chemical Technology & Biotechnology, 67(1), 1-14, 1996.
21. Lewis DL, Garrison AW, Wommack KE, Whittemore A, Steudler P, Melillo J. "Influence of environmental changes on degradation of chiral pollutants in soils". Nature, 401(6756), 898-901, 1999.
22. Buerge IJ, Bächli A, Heller WE, Keller M, Poiger T. "Environmental behavior of the chiral herbicide haloxyfop. 2. unchanged enantiomer composition in blackgrass (Alopecurus myosuroides) and garden cress (Lepidium sativum)". Journal of Agricultural and Food Chemistry, 63(10), 2591-2596, 2015.
23. Hühnerfuss H, Faller J, Koenig WA, Ludwig P. "Gas chromatographic separation of the enantiomers of marine pollutants. 4. fate of hexachlorocyclohexane ısomers in the baltic and north sea". Environmental Science & Technology, 26(11), 2127-2133, 1992.
24. Wong CS. "Environmental fate processes and biochemical transformations of chiral emerging organic pollutants". Analytical and Bioanalytical Chemistry, 386(3), 544-558, 2006.
25. Williams A. "Opportunities for chiral agrochemicals". Pesticide Science, 46(1), 3-9, 1996.
26. Thurman EM, Goolsby DA, Meyer MT, Kolpin DW. "Herbicides in surface waters of the midwestern united states: The effect of spring flush". Environmental Science & Technology, 25(10), 1794-1796, 1991.
27. Jantunen LM, Helm PA, Ridal JJ, Bidleman TF. "Air-Water gas exchange of chiral and achiral organochlorine pesticides in the great lakes". Atmospheric Environment, 42(36), 8533-8542, 2008.
28. Perez-Fernandez V, Garcia MA, Marina ML. "Characteristics and enantiomeric analysis of chiral pyrethroids". Journal of Chromatography A, 1217(7), 968-989, 2010.
29. Lehmler HJ, Harrad SJ, Huhnerfuss H, Kania-Korwel I, Lee CM, Lu Z, Wong CS. "Chiral polychlorinated biphenyl transport, metabolism and distribution: A review". Environmental Science & Technology, 44(8), 2757-2766, 2010.
30. Miralles-Marco A, Harrad S. "Perfluorooctane sulfonate: A review of human exposure, biomonitoring and the environmental forensics utility of its chirality and ısomer distribution". Environment International, 77, 148-159, 2015.
31. Hühnerfuss H. Shah MR. "Enantioselective chromatography-a powerful tool for the discrimination of biotic and abiotic transformation processes of chiral environmental pollutants". Journal of Chromatography A, 1216(3), 481-502, 2009.
32. Li Y, Dong F, Liu X, Xu J, Han Y, Zheng Y. "Enantioselectivity in tebuconazole and myclobutanil non-target toxicity and degradation in soils". Chemosphere, 122, 145-153, 2015.
33. Ribeiro A, Castro PL, Tiritan M. "Chiral pharmaceuticals in the environment". Environmental Chemistry Letters, 10(3), 239-253, 2012.
34. Aturki Z, Rocco A, Rocchi S, Fanali S. "Current applications of miniaturized chromatographic and electrophoretic techniques in drug analysis". Journal of Pharmaceutical and Biomedical Analysis, 101, 194-220, 2014.
35. Amini A. "Recent developments in chiral capillary electrophoresis and applications of this technique to pharmaceutical and biomedical analysis". Electrophoresis, 22(15), 3107-3130, 2001.
36. Fanali S. "Identification of chiral drug ısomers by capillary electrophoresis". Journal of Chromatography A, 735(1), 77-121, 1996.
37. Ma Y, Zhang H, Chen H, Chen X. "Recent developments in chiral analysis of β‐blocker drugs by capillary electromigration techniques". Electrophoresis, 35(23), 3345-3354, 2014.
38. Ribeiro AR, Maia AS, Cass QB, Tiritan ME. "Enantioseparation of chiral pharmaceuticals in biomedical and environmental analyses by liquid chromatography: An overview". Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences, 968, 8-21, 2014.
39. Wan H, Blomberg LG. "Chiral separation of amino acids and peptides by capillary electrophoresis". Journal of Chromatography A, 875(1), 43-88, 2000.
40. Chen B, He M, Zhong C, Hu B. "Chiral speciation of selenoamino acids in biological samples". Journal of Chromatography A, 1363, 62-70, 2014.
41. Bicchi C, D’Amato A, Rubiolo P. "Cyclodextrin derivatives as chiral selectors for direct gas chromatographic separation of enantiomers in the essential oil, aroma and flavour fields". Journal of Chromatography A, 843(1), 99-121, 1999.
42. Perez-Fernandez V, Garcia MA, Marina ML. "Chiral separation of agricultural fungicides". Journal of Chromatography A, 1218(38), 6561-6582, 2011.
43. Kodama S, Saito Y, Chinaka S, Yamamoto A, Hayakawa K. "Chiral capillary electrophoresis of agrochemicals in real samples". Journal of Health Science, 52(5), 489-494, 2006.
44. Garrison AW, Schmitt P, Martens D, Kettrup A. "Enantiomeric selectivity in the environmental degradation of dichlorprop as determined by high-performance capillary electrophoresis". Environmental Science & Technology, 30(8), 2449-2455, 1996.
45. Ettre L. "Nomenclature for chromatography (IUPAC recommendations 1993)". Pure and Applied Chemistry, 65(4), 819-872, 1993.
46. Poole CF. The Essence of Chromatography. 1st ed. Amsterdam, Netherlands, Elsevier Science, 2003.
47. Gil-Av E, Feibush B, Charles-Sigler R. "Separation of enantiomers by gas liquid chromatography with an optically active stationary phase". Tetrahedron Letters, 7(10), 1009-1015, 1966.
48. Gübitz G, Schmid MG. "Chiral separation by chromatographic and electromigration techniques. A review". Biopharmaceutics & Drug Disposition, 22(7-8), 291-336, 2001.
49. Aboul-Enein HY, Ali I. "Analysis of the chiral pollutants by chromatography". Toxicological & Environmental Chemistry, 86(1), 1-22, 2004.
50. Koscielski T, Sybilska D, Jurczak J. "Separation of alpha-pinene and beta-pinene into enantiomers in gas-liquid-chromatography systems via alpha-cyclodextrin ınclusion complexes". Journal of Chromatography, 280(1), 131-134, 1983.
51. König W, Krebber R, Mischnick P. "Cyclodextrins as chiral stationary phases in capillary gas chromatography. Part V: Octakis (3-O-Butyryl‐2, 6‐di‐O‐pentyl)‐γ‐Cyclodextrin". Journal of High Resolution Chromatography, 12(11), 732-738, 1989.
52. Vetter W. "Enantioselective fate of chiral chlorinated hydrocarbons and their metabolites in environmental samples". Food Reviews International, 17(2), 113-182, 2001.
53. Hashim NH, Shafie S, Khan SJ. "Enantiomeric fraction as an indicator of pharmaceutical biotransformation during wastewater treatment and in the environment-a review". Environmental Technology, 31(12), 1349-1370, 2010.
54. Sekhon BS. "Chiral pesticides". Journal of Pesticide Science, 34(1), 1-12, 2009.
55. Harner T, Wiberg K, Norstrom R. "Enantiomer fractions are preferred to enantiomer ratios for describing chiral signatures in environmental analysis". Environmental Science & Technology, 34(1), 218-220, 2000.
56. Vetter W, Schurig V. "Enantioselective determination of chiral organochlorine compounds in biota by gas chromatography on modified cyclodextrins". Journal of Chromatography A, 774(1-2), 143-175, 1997.
57. Jantunen LM, Bidleman TF. "Organochlorine pesticides and enantiomers of chiral pesticides in arctic ocean water". Archives of Environmental Contamination and Toxicology, 35(2), 218-228, 1998.
58. Kurt-Karakus PB, Bidleman TF, Jantunen LM, Jones KC. Environmental Fate of Legacy Chiral Pesticides in Background Soils. Editors: Mehmetli E, Koumanova B. The Fate of Persistent Organic Pollutants in the Environment, 99-112, Netherlands, Springer, 2008.
59. Kurihara N, Miyamoto J. Chirality in Agrochemicals. 5th ed. New York, USA, Wiley, 1998.
60. Easson LH, Stedman E. "Studies on the relationship between chemical constitution and physiological action: Molecular dissymmetry and physiological activity". Biochemical Journal, 27(4), 1257-1266, 1933.
61. Kohler HPE, Nickel K, Zipper C. "Effect of chirality on the microbial degradation and the environmental fate of chiral pollutants". Advances in Microbial Ecology, 16, 201-231, 2000.
62. Mesecar AD, Koshland DE. "Structural biology: A new model for protein stereospecificity". Nature, 403(6770), 614-615, 2000.
63. Chen W, Mulchandani A. "The use of live biocatalysts for pesticide detoxification". Trends in Biotechnology, 16(2), 71-76, 1998.
64. Smith SW. "Chiral toxicology: It's the same thing only different". Toxicological Sciences, 110(1), 4-30, 2009.
65. Schneiderheinze J, Armstrong D, Berthod A. "Plant and soil enantioselective biodegradation of racemic phenoxyalkanoic herbicides". Chirality, 11(4), 330-337, 1999.
66. Schmitt P, Garrison A, Freitag D, Kettrup A. "Application of cyclodextrin-modified micellar electrokinetic chromatography to the separations of selected neutral pesticides and their enantiomers". Journal of Chromatography A, 792(1), 419-429, 1997.
67. Huang L, Lu D, Diao J, Zhou Z. "Enantioselective toxic effects and biodegradation of benalaxyl in scenedesmus obliquus". Chemosphere, 87(1), 7-11, 2012.
68. Kohler HPE, Angst W, Giger W, Kanz C, Müller S, Suter MJF. "Environmental fate of chiral pollutants-the necessity of considering stereochemistry". CHIMIA International Journal for Chemistry, 51(12), 947-951, 1997.
69. Wong F, Robson M, Diamond M, Harrad S, Truong J. "Concentrations and chiral signatures of pops in soils and sediments: a comparative urban versus rural study in Canada and UK". Chemosphere, 74(3), 404-411, 2009.
70. Jamshidi A, Hunter S, Hazrati S, Harrad S. "Concentrations and chiral signatures of polychlorinated biphenyls in outdoor and ındoor air and soil in a major UK conurbation". Environmental Science & Technology, 41(7), 2153-2158, 2007.
71. Aigner EJ, Leone AD, Falconer RL. "Concentrations and enantiomeric ratios of organochlorine pesticides in soils from the US corn belt". Environmental Science & Technology, 32(9), 1162-1168, 1998.
72. Wiberg K, Harner T, Wideman JL, Bidleman TF. "Chiral analysis of organochlorine pesticides in alabama soils". Chemosphere, 45(6), 843-848, 2001.
73. Kurt-Karakus PB, Bidleman TF, Jones KC. "Chiral organochlorine pesticide signatures in global background soils". Environmental Science & Technology, 39(22), 8671-8677, 2005.
74. Hühnerfuss H, Pfaffenberger B, Gehrcke B, Karbe L, Konig WA, Landgraff O. "Gas chromatographic enantiomer separation and potential toxicity of atropisomeric polychlorinated biphenyls in marine biota: Has the toxic equivalence factor (TEF) concept to be expanded?". Organohalogen Compounds, 21, 15-20, 1994.
75. Faller J, Hühnerfuss H, König WA, Ludwig P. "Gas chromatographic separation of the enantiomers of marine organic pollutants: Distribution of α-HCH enantiomers in the north sea". Marine Pollution Bulletin, 22(2), 82-86, 1991.
76. Ludwig P, Huhnerfuss H, Konig WA, Gunkel W. "Gas-Chromatographic separation of the enantiomers of marine pollutants. 3. enantioselective degradation of alpha-hexachlorocyclohexane and gamma-hexachlorocyclohexane by marine microorganisms". Marine Chemistry, 38(1-2), 13-23, 1992.
77. Hühnerfuss H, Kallenborn R. "Chromatographic-separation of marine organic pollutants". Journal of Chromatography-Biomedical Applications, 580(1-2), 191-214, 1992.
78. Jantunen LM, Bidleman TF. "Differences in enantioselective degradation of α-hexachlorocyclohexane in the bering-chukchi seas and the arctic ocean". Organohalogen Compounds, 24, 425-428, 1995.
79. Wood AW, Chang RL, Levin W, Thomas PE, Ryan D, Stoming TA, Thakker DR, Jerina DM, Conney AH. "Metabolic activation of 3-methylcholanthrene and its metabolites to products mutagenic to bacterial and mammalian cells". Cancer Research, 38(10), 3398-3404, 1978.
80. Erdogrul O, Covaci A, Schepens P. "Levels of organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in fish species from Kahramanmaras, Turkey". Environment International, 31(5), 703-711, 2005.
81. Li J, Zhang G, Qi S, Li X, Peng X. "Concentrations, enantiomeric compositions and sources of HCH, DDT and chlordane in soils from the pearl river delta, South China". Science of the Total Environment, 372(1), 215-224, 2006.
82. Mattina MJI, White J, Eitzer B, Iannucci‐Berger W. "Cycling of weathered chlordane residues in the environment: Compositional and Chiral Profiles in Contiguous Soil, Vegetation, and Air Compartments". Environmental Toxicology and Chemistry, 21(2), 281-288, 2002.
83. Falconer RL, Leone AD, Bodnar C, Wiberg K, Bidleman TF, Jantunen LM, Harner T, Parkhurst WJ, Alegria H, Brice K, Su K. "Using enantiomeric ratios to determine sources of chlordane to ambient air". Organohalogen Compounds, 35, 331-334, 1998.
84. Bidleman T, Jantunen L, Wiberg K, Harner T, Brice K, Su K, Falconer R, Leone A, Aigner E, Parkhurst W. "Soil as a source of atmospheric heptachlor epoxide". Environmental Science & Technology, 32(10), 1546-1548, 1998.
85. Hühnerfuss H, Faller J, Kallenborn R, König WA, Ludwig P, Pfaffenberger B, Oehme M, Rimkus G. "Enantioselective and nonenantioselective degradation of organic pollutants in the marine ecosystem". Chirality, 5(5), 393-399, 1993.
86. Franke S, Meyer C, Heinzel N, Gatermann R, Hühnerfuss H, Rimkus G, König WA, Francke W. "Enantiomeric composition of the polycyclic musks HHCB and AHTN in different aquatic species". Chirality, 11(10), 795-801, 1999.
87. Vetter W, Bartha R, Stern G, Tomy G. "Enantioselective determination of two major compounds of technical toxaphene in canadian lake sediment cores from the last 60 years". Organohalogen Compounds, 35, 343-346, 1998.
88. Wong CS, Garrison AW, Foreman WT. "Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic bed sediment". Environmental Science & Technology, 35(1), 33-39, 2001.
89. Wong CS, Garrison AW, Smith PD, Foreman WT. "Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic and riparian biota". Environmental Science & Technology, 35(12), 2448-2454, 2001.
90. Lu Z, Fisk AT, Kovacs KM, Lydersen C, McKinney MA, Tomy GT, Rosenberg B, McMeans BC, Muir DCG, Wong CS. "Temporal and spatial variation in polychlorinated biphenyl chiral signatures of the greenland shark (Somniosus microcephalus) and its arctic marine food web". Environmental Pollution, 186, 216-225, 2014.
91. Bidleman TF, Jantunen LM, Hung H, Ma J, Stern GA, Rosenberg B, Racine J. "Annual cycles of organochlorine pesticide enantiomers in arctic air suggest changing sources and pathways". Atmospheric Chemistry and Physics, 15(3), 1411-1420, 2015.
92. Sun M, Liu D, Shen Z, Zhou Z, Wang P. "Stereoselective quantitation of haloxyfop in environment samples and enantioselective degradation in soils". Chemosphere, 119, 583-589, 2015.
93. Bidleman TF, Jantunen LM, Kurt-Karakus PB, Wong F. "Chiral persistent organic pollutants as tracers of atmospheric sources and fate: Review and prospects for ınvestigating climate change ınfluences". Atmospheric Pollution Research, 3(4), 371-382, 2012.
94. Zhang A, Liu W, Yuan H, Zhou S, Su Y, Li YF. "Spatial distribution of hexachlorocyclohexanes in agricultural soils in zhejiang province, China, and correlations with elevation and temperature". Environmental Science & Technology, 45(15), 6303-6308, 2011.
95. Buerge IJ, Poiger T, Mueller MD, Buser HR. "Influence of pH on the stereoselective degradation of the fungicides epoxiconazole and cyproconazole in soils". Environmental Science & Technology, 40(17), 5443-5450, 2006.
96. Buser HR, Müller MD. "Occurrence and transformation reactions of chiral and achiral phenoxyalkanoic acid herbicides in lakes and rivers in Switzerland". Environmental Science & Technology, 32(5), 626-633, 1998.
97. Li Z, Zhang Y, Li Q, Wang W, Li J. "Enantioselective degradation, abiotic racemization, and chiral transformation of triadimefon in soils". Environmental Science & Technology, 45(7), 2797-2803, 2011.
98. Vasskog T, Bergersen O, Anderssen T, Jensen E, Eggen T. "Depletion of selective serotonin reuptake ınhibitors during sewage sludge composting". Waste Management, 29(11), 2808-2815, 2009.
99. Carballa M, Omil F, Lema JM, Llompart M, Garcia-Jares C, Rodriguez I, Gomez M, Ternes T. "Behavior of pharmaceuticals, cosmetics and hormones in a sewage treatment plant". Water Research, 38(12), 2918-2926, 2004.
100. Wu C, Spongberg AL, Witter JD, Fang M, Ames A, Czajkowski KP. "Detection of pharmaceuticals and personal care products in agricultural soils receiving biosolids application". CLEAN-Soil, Air, Water, 38(3), 230-237, 2010.
101. Moreira IS, Ribeiro AR, Afonso CM, Tiritan ME, Castro PM. "Enantioselective biodegradation of fluoxetine by the bacterial strain labrys portucalensis F11". Chemosphere, 111, 103-111, 2014.
102. Bidleman TF, Jantunen LM, Kurt-Karakus PB, Wong F, Hung H, Ma J, Stern G, Rosenberg B. "Chiral chemicals as tracers of atmospheric sources and fate processes in a world of changing climate". Mass Spectrometry, 2(Special Issue), S0019, 2013.