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Fate and transport of chlormequat in subsurface environments

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Abstract

Background, aim and scope

Chlormequat (Cq) is a plant growth regulator used throughout the world. Despite indications of possible effects of Cq on mammalian health and fertility, little is known about its fate and transport in subsurface environments. The aim of this study was to determine the fate of Cq in three Danish subsurface environments, in particular with respect to retardation of Cq in the A and B horizons and the risk of leaching to the aquatic environment. The study combines laboratory fate studies of Cq sorption and dissipation with field scale monitoring of the concentration of Cq in the subsurface environment, including artificial drains.

Materials and methods

For the laboratory studies, soil was sampled from the A and B horizons at three Danish field research stations—two clayey till sites and one coarse sandy site. Adsorption and desorption were described by means of the distribution coefficient (K d) and the Freundlich adsorption coefficient (K F,ads). The dissipation rate was estimated using soil sampled from the A horizon at the three sites. Half life (DT50) was calculated by approximation to first-order kinetics. A total of 282 water samples were collected at the sites under the field monitoring study— groundwater from shallow monitoring screens located 1.5–4.5 m b.g.s. at all three sites as well as drainage water from the two clayey sites and porewater from suction cups at the sandy site, in both cases from 1 m b.g.s. The samples were analysed using LC-MS/MS. The field monitoring study was supported by hydrological modelling, which provided an overall water balance and a description of soil water dynamics in the vadose zone.

Results

The DT50 of Cq from the A horizon ranged from 21 to 61 days. The Cq concentration-dependant distribution coefficient (K d) ranged from 2 to 566 cm3/g (median 18 cm3/g), and was lowest in the sandy soil (both the A and B horizons). The K F,ads ranged from 3 to 23 (µg1 − 1/n (cm3)1/n g−1) with the exponent (1/n) ranging from 0.44 to 0.87, and was lowest in the soil from the sandy site. Desorption of Cq was very low for the soil types investigated (<10%w). Cq in concentrations exceeding the detection limit (0.01 µg/L) was only found in two of the 282 water samples, the highest concentration being 0.017 µg/L.

Discussion

That sorption was highest in the clayey till soils is attributable to the composition of the soil, the soil clay and iron content being the main determinant of Cq sorption in both the A and B horizons of the subsurface environment. Cq was not detected in concentrations exceeding the detection limit in either the groundwater or the porewater at the sandy site. The only two samples in which Cq was detected were drainage water samples from the two clayey till sites. The presence of Cq here was probably attributable to the hydrogeological setting as water flow at the two clayey till sites is dominated by macropore flow and less by the flow in the low permeability matrix. In contrast, water flow at the sandy site is dominated by matrix flow in the high permeability matrix, with negligible macropore flow. Given the characteristics of these field sites, Cq adsorption and desorption can be expected to be controlled by the clay composition and content and the iron content. Combining these observations with the findings of the sorption and dissipation studies indicates that the key determinant of Cq retardation and fate in the soil is sorption characteristics and bioavailability.

Conclusions

The leaching risk of Cq was negligible at the clayey till and sandy sites investigated. The adsorption and desorption experiments indicated that absorption of Cq was high at all three sites, in particular at the clayey till sites, and that desorption was generally very limited. The study indicates that leaching of Cq to the groundwater is hindered by sorption and dissipation. The detection of Cq in drainage water at the clayey till sites and the evidence for rapid transport through macropores indicate that heavy precipitation events may cause pulses of Cq.

Recommendations and perspectives

The present study is the first to indicate that the risk of Cq leaching to the groundwater and surface water is low. Prior to any generalisation of the present results, the fate of Cq needs to be studied in other soil types, application regimes and climatic conditions to determine the Cq retardation capacity of the soils. The study identifies bioavailability and heavy precipitation events as important factors when assessing the risk of Cq contamination of the aquatic environment. The possible effects of future climate change need to be considered when assessing whether or not Cq poses an environmental risk.

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References

  • Alder L, Startin JR (2005) Determination of chlormequat and mepiquat in foods by liquid chromatography/mass spectrometry or liquid chromatography/tandem mass spectrometry: interlaboratory study. J AOAC Int 88:1762–1776

    CAS  Google Scholar 

  • Alexopoulos AA, Akoumianakis KA, Passam HC (2006) Effect of plant growth regulators on the tuberisation and physiological age of potato (Solanum tuberosum L.) tubers grown from true potato seed. Can J Plant Sci 86:1217–1225

    CAS  Google Scholar 

  • Andersen HR, Vinggaard AM, Rasmussen TH, Gjermandsen IM, Bonefeld-Jorgensen EC (2002) Effects of currently used pesticides in assays for estrogenicity, androgenicity, and aromatase activity in vitro. Toxicol Appl Pharmacol 179:1–12

    Article  CAS  Google Scholar 

  • Andersen JH, Bille RLL, Granby K (2007) An intercomparison study of the determination of glyphosate, chlormequat and mepiquat residues in wheat. Food Addit Contam 24:140–148

    Article  CAS  Google Scholar 

  • Anonymous (1999a) The pesticide manual, 11th edn. British Crop Protection Council, Surrey

    Google Scholar 

  • Anonymous (1999b) Soil taxonomy—a basic system of soil classification for making and interpreting soil surveys, 2nd edn. USDA-NRCS Agricultural Handbook, vol 436. United States Department of Agriculture, New York

    Google Scholar 

  • Anonymous (2000) Adsorption-desorption using a batch equilibrium method. Section 1: physical chemical properties, 106, OECD guideline for the testing of chemicals. OECD, Paris

    Google Scholar 

  • Anonymous (2006) Reregistration eligibility decision for aliphatic alkyl quaternaries (DDAC). EPA-HQ-OPP-2006-0338/EPA 739-R-06-008. US Environmental Protection Agency, Prevention, Pesticides and Toxic Substances, Washington, D.C.

  • Anonymous (2007a) The use of plant protection products in the European Union, data 1992-2003. Nadin, Pierre. http://epp.eurostat.ec.europa.eu. ISBN 92-79-03890-7. Eurostat, European Communities, Luxembourg

  • Anonymous (2007b) Reregistration eligibility decision for chlormequat chloride (RED). EPA-HQ-OPP-2007-0968/EPA 738-R-07-014. US Environmental Protection Agency, Prevention, Pesticides and Toxic Substances, Washington, D.C.

  • Aramendia MA, Borau V, Lafont F, Marinas A, Marinas JM, Moreno JM, Urbano FJ (2007) Determination of herbicide residues in olive oil by gas chromatography–tandem mass spectrometry. Food Chem 105:855–861

    Article  CAS  Google Scholar 

  • Barbash JE (2007) The geochemistry of pesticides 9.15. In: Holland HD, Turekian KK (eds) Treatise on geochemistry. Oxford, Pergamon, pp 1–43

    Chapter  Google Scholar 

  • Barlebo HC, Rosenbom AE, and Kjaer J (2007) Evaluation of pesticide scenarios for the registration procedure. Environmental Project No. 1178, Danish Environmental Protection Agency, Copenhagen

  • Berry PM, Sterling M, Spink JH, Baker CJ, Sylvester-Bradley R, Mooney SJ, Tams AR, Ennos AR (2004) Understanding and reducing lodging in cereals. Adv Agron Vol 84(84):217–271

    Google Scholar 

  • Bethke CM, Brady PV (2000) How the Kd approach undermines ground water cleanup. Ground Water 38:435–443

    Article  CAS  Google Scholar 

  • Beulke S, Brown CD (2001) Evaluation of methods to derive pesticide degradation parameters for regulatory modelling. Biol Fert Soils 33:558–564

    Article  CAS  Google Scholar 

  • Browne RA, White EM, Burke JI (2006) Responses of developmental yield formation processes in oats to variety, nitrogen, seed rate and plant growth regulator and their relationship to quality. J Agr Sci 144:533–545

    Article  CAS  Google Scholar 

  • de Jonge LW, Kjaergaard C, Moldrup P (2004) Colloids and colloid-facilitated transport of contaminants in soils: an introduction. Vadose Zone J 3:321–325

    Article  Google Scholar 

  • Dekhuijz HM, Vonk CR (1974) Distribution and degradation of chlormequat in wheat plants. Pestic Biochem Physiol 4:346–355

    Article  Google Scholar 

  • Esparza X, Moyano E, Galceran MT (2009) Analysis of chlormequat and mepiquat by hydrophilic interaction chromatography coupled to tandem mass spectrometry in food samples. J Chromatogr A 1216:4402–4406

    Article  CAS  Google Scholar 

  • Espindula MC, Rocha VS, Grossi JAS, Souza MA, Souza LT, Favarato LF (2009) Use of growth retardants in wheat. Planta Daninha 27:379–387

    Article  Google Scholar 

  • Fairbrother A, Yuill TM, Olson LJ (1986) Effects of three plant growth regulators on the immune-response of young and aged deer mice Peromyscus Maniculatus. Arch Environ Contam Toxicol 15:265–275

    Article  CAS  Google Scholar 

  • Flury M (1996) Experimental evidence of transport of pesticides through field soils—a review. J Environ Qual 25:25–45

    Article  CAS  Google Scholar 

  • Gencsoylu I (2009) Effect of plant growth regulators on agronomic characteristics, lint quality, pests, and predators in cotton. J Plant Growth Regul 28:147–153

    Article  CAS  Google Scholar 

  • Gevao B, Semple KT, Jones KC (2000) Bound pesticide residues in soils: a review. Environ Pollut 108:3–14

    Article  CAS  Google Scholar 

  • Giles CH, MacEwan TH, Nakhwa SN, Smith D (1960) Studies in adsorption. Part XI. A system of classification of solution adsorption isotherms, and its use in diagnosis of adsorption mechanisms and in measurement of specific surface areas of soil. J Chem Soc 4:3973–3993

    Article  Google Scholar 

  • Gocer M, Hoferer K, Zipfel J, Spangenberg B (2009) A new TLC method for quantification of paraquat, diquat, difenzoquat, mepiquat and chloromequat in water. J Planar Chromatogr—Mod TLC 22:59–63

    Article  CAS  Google Scholar 

  • Granby K, Vahl M (2001) Investigation of the herbicide glyphosate and the plant growth regulators chlormequat and mepiquat in cereals produced in Denmark. Food Addit Contam 18:898–905

    Article  CAS  Google Scholar 

  • Hauptman S, Bier H, Faust H (1969) Chemistry of 2-chloroethyltrimethyl ammonium chloride (in German). J Prakt Chem 311:705–711

    Article  Google Scholar 

  • Henriksen T, Juhler RK, Brandt G, Kjaer J (2009) Analysis of the plant growth regulator chlormequat in soil and water using liquid chromatography tandem mass-spectrometry (LC-MS/MS), pressurised liquid extraction, and solid phase extraction. J Chromatogr A 1216:2504–2510

    Article  CAS  Google Scholar 

  • Hughes RG (1967) Chlormequat to control lodging in wheat. Agriculture 74:133

    Google Scholar 

  • Jarvis NJ (2007) A review of non-equilibrium water flow and solute transport in soil macropores: principles, controlling factors and consequences for water quality. Eur J Soil Science 58:523–546

    Article  Google Scholar 

  • Jin F, Hu HY, Yang M, Jin XH, He WJ, Han HD (2006) Determination of diallyldimethylammonium chloride in drinking water by reversed-phase ion-pair chromatography-electrospray ionization mass spectrometry. J Chromatogr A 1101:222–225

    Article  CAS  Google Scholar 

  • Juhler RK, Henriksen TH, Ernstsen V, Vinther FP, Rosenberg P (2008) Impact of basic soil parameters on pesticide disappearance investigated by multivariate partial least square regression and statistics. J Environ Qual 37:1719–1732

    Article  CAS  Google Scholar 

  • Juhler RK, Vahl M (1999) Residues of chlormequat and mepiquat in grain—results from the Danish National Pesticide Survey. J AOAC Int 82:331–336

    CAS  Google Scholar 

  • Kamel AH, Moreira FTC, Almeida SAA, Sales MGF (2008) Novel potentiometric sensors of molecular imprinted polymers for specific binding of chlormequat. Electroanalysis 20:194–202

    Article  CAS  Google Scholar 

  • Kjaer J, Olsen P, Bach K, Barlebo HC, Ingerslev F, Hansen M, Sorensen BH (2007) Leaching of estrogenic hormones from manure-treated structured soils. Environ Sci Technol 41:3911–3917

    Article  CAS  Google Scholar 

  • Kjaer J, Olsen P, Ullum M, Grant R (2005) Leaching of glyphosate and amino-methylphosphonic acid from Danish agricultural field sites. J Environ Qual 34:608–620

    Article  CAS  Google Scholar 

  • Kookana RS, Aylmore LAG (1993) Retention and release of diquat and paraquat herbicides in soils. Aust J Soil Res 31:97–109

    Article  CAS  Google Scholar 

  • Kramers PGN, Knaap AGAC, Voogd CE (1975) Lack of mutagenicity of chlormequat chloride in Drosophila and in bacteria. Mutat Res 31:65–68

    CAS  Google Scholar 

  • Langhammer M, Kuhla S, Schneider F, Renne U, Spitschak M, Hagemeister H (1999) Effects of chlorocholine chloride-treated wheat on special fertility traits in laboratory mice. J Anim Physiol An N 81:190–202

    CAS  Google Scholar 

  • Larsbo M, Roulier S, Stenemo F, Kasteel R, Jarvis N (2005) An improved dual-permeability model of water flow and solute transport in the vadose zone. Vadose Zone J 4:398–406

    Article  Google Scholar 

  • Leffers H, Hansen M, Sorensen MT, Guillette L, Tuomisto J, Jensen AA, Bjerregaard P (2006) Effects of the plant growth regulator, chlormequat, on mammalian fertility—discussion. Int J Androl 29:129–133

    Article  CAS  Google Scholar 

  • Leitch MH, Kurt O (1999) Effects of plant growth regulators on stem extension and yield components of linseed (Linum usitatissimum). J Agr Sci 132:189–199

    Article  CAS  Google Scholar 

  • Lesueur C, Gartner M, Mentler A, Fuerhacker M (2007) Qualitative and quantitative analysis of polar pesticide multiresidues in leaf samples with a liquid chromatography-ion-trap mass-selective detector. Int J Environ Anal Chem 87:1013–1032

    CAS  Google Scholar 

  • Lindhardt B, Abiltrup C, Vosgerau H, Olsen P, Torp S, Iversen BV, Jørgensen OJ, Plauborg F, Rasmussen P, Gravesen P (2001) The Danish Pesticide Leaching Assessment Programme, Site characterization and monitoring design. Geological Survey of Denmark and Greenland, GEUS, Copenhagen

    Google Scholar 

  • Liu L, Tindall JA, Friedel MJ, Zhang WX (2007) Biodegradation of organic chemicals in soil/water microcosms system: model development. Wat Air Soil Poll 178:131–143

    Article  CAS  Google Scholar 

  • Lopez-Paz JL, Catala-Icardo M, Anton-Garrido B (2009) Determination of diquat by flow injection–chemiluminescence. Anal Bioanal Chem 394:1073–1079

    Article  CAS  Google Scholar 

  • Marchese S, Perret D, Bafile E, Gentili A, Caretti F, Berardino M (2009) Pressurized liquid extraction coupled with LC-ESI-MS-MS for the determination of herbicides chlormequat and mepiquat in flours. Chromatographia 70:761–767

    Article  CAS  Google Scholar 

  • Maqueda C, Morillo E (2001) Sorption of chlormequat on montmorillonite as affected by dissolved copper. Influence of background electrolytes. Clay Miner 36:473–481

    Article  CAS  Google Scholar 

  • Maza J, Jimenezlopez A, Bruque S (1989) Interaction of chlorocholine chloride with montmorillonite. Soil Sci 147:11–16

    Article  CAS  Google Scholar 

  • McKeague JA, Day JH (1966) Dithionite- and oxalate-extractable Fe and Al as aids in differentiating various classes of soils. Can J Soil Sci 46:13–22

    Article  CAS  Google Scholar 

  • Nurhayati CS, Chaidir ERA, Ebel R, ter Meulen U (2006) The metabolite products of chlorocholine chloride (CCC) in eggs and meat of laying hens fed N-15-CCC containing diets. J Anim Physiol Anim Nutr 90:165–172

    Article  CAS  Google Scholar 

  • Olson LJ, Hinsdill RD (1984) Influence of feeding chlorocholine chloride and glyphosine on selected immune parameters in deer mice, Peromyscus maniculatus. Toxicology 30:103–114

    Article  CAS  Google Scholar 

  • Pateiro-Moure M, Martinez-Carballo E, Arias-Estevez M, Simal-Gandara J (2008) Determination of quaternary ammonium herbicides in soils—comparison of digestion, shaking and microwave-assisted extractions. J Chromatogr A 1196:110–116

    Article  CAS  Google Scholar 

  • Pateiro-Moure M, Perez-Novo C, Arias-Estevez M, Rial-Otero R, Simal-Gandara J (2009) Effect of organic matter and iron oxides on quaternary herbicide sorption–desorption in vineyard-devoted soils. J Colloid Interface Sci 333:431–438

    Article  CAS  Google Scholar 

  • Pico Y, Font G, Ruiz MJ, Fernandez M (2006) Control of pesticide residues by liquid chromatography–mass spectrometry to ensure food safety. Mass Spectrom Rev 25:917–960

    Article  CAS  Google Scholar 

  • Poulsen ME, Christensen HB, Sorensen MT, Leffers H, Andersen JH (2007) Determination of chlormequat in pig serum and sow milk by LC-MS/MS. Anal Bioanal Chem 389:1799–1804

    Article  CAS  Google Scholar 

  • Rademacher W (2000) Growth retardants: effects on gibberellin biosynthesis and other metabolic pathways. Annu Rev Plant Phys 51:501–531

    Google Scholar 

  • Reardon EJ (1981) Kd’s—can they be used to describe reversible ion sorption reactions in contaminant migration. Ground Water 19:279–286

    Article  CAS  Google Scholar 

  • Reynolds SL, Hill ARC, Thomas MR, Hamey PY (2004) Occurrence and risks associated with chlormequat residues in a range of foodstuffs in the UK. Food Addit Contam 21:457–471

    Article  CAS  Google Scholar 

  • Rhodes D, Hanson AD (1993) Quaternary ammonium and tertiary sulfonium compounds in higher plants. Annu Rev Plant Phys 44:357–384

    Article  CAS  Google Scholar 

  • Rosenbom AE, Ernstsen V, Fluhler H, Jensen KH, Refsgaard JC, Wydler H (2008) Fluorescence imaging applied to tracer distributions in variably saturated fractured clayey till. J Environ Qual 37:448–458

    Google Scholar 

  • Rytwo G, Tropp D (2001) Improved efficiency of a divalent herbicide in the presence of clay, by addition of monovalent organocations. Appl Clay Sci 18:327–333

    Article  CAS  Google Scholar 

  • Rytwo G, Tropp D, Serban C (2002) Adsorption of diquat, paraquat and methyl green on sepiolite: experimental results and model calculations. Appl Clay Sci 20:273–282

    Article  CAS  Google Scholar 

  • Smith MC, Shaw DR, Massey JH, Boyette M, Kingery W (2003) Using nonequilibrium thin-disc and batch equilibrium techniques to evaluate herbicide sorption. J Environ Qual 32:1393–1404

    Article  CAS  Google Scholar 

  • Sorensen MT, Danielsen V (2006) Effects of the plant growth regulator, chlormequat, on mammalian fertility. Int J Androl 29:129–132

    Article  CAS  Google Scholar 

  • Sorensen MT, Poulsen ME, Leffers H, Vajta G, Halekoh U (2009) No effect of the plant growth regulator, chlormequat, on boar fertility. Animal 3:697–702

    Article  CAS  Google Scholar 

  • Stenrod M, Heggen HE, Bolli RI, Eklo OM (2008) Testing and comparison of three pesticide risk indicator models under Norwegian conditions—a case study in the Skuterud and Heiabekken catchments. Agr Ecosyst Environ 123:15–29

    Article  CAS  Google Scholar 

  • Sussmuth R, Lingens F (1976) Mutagenic actions of chlorocholine chloride. Mutat Res 40:229–235

    Article  CAS  Google Scholar 

  • Tolbert NE (1960) (2-Chloroethyl)trimethylammonium chloride and related compounds as plant growth substances. II. Effect on growth of wheat. Plant Physiol 35:380–385

    Article  CAS  Google Scholar 

  • Torner H, Blottner S, Kuhla S, Langhammer M, Alm H, Tuchscherer A (1999) Influence of chlorocholinechloride-treated wheat on selected in vitro fertility parameters in male mice. Reprod Toxicol 13:399–404

    Article  CAS  Google Scholar 

  • Ueberschar KH, Danicke S, Wolff J (2003) Gaschromatic determination of chlormequat in silo cereals and bran. Landbauforsch Volk 53:37–42

    Google Scholar 

  • Vahl M, Graven A, Juhler RK (1998) Analysis of chlormequat residues in grain using liquid-chromatography mass–spectrometry (LC-MS/MS). Fresenius J Anal Chem Vol 361: 817–820

    Article  CAS  Google Scholar 

  • Wang JH, Lu XY, Huang M, Wu Z, Ma GP, Xu CY (2007) Rapid screening and confirmation of chlormequat and mepiquat residues in tomato and its products using liquid chromatography with electrospray tandem mass spectrometry. Chin J Anal Chem 35:1509–1512

    CAS  Google Scholar 

  • Yamano T, Morita S (1993) Effects of pesticides on isolated rat hepatocytes, mitochondria, and microsomes. Arch Environ Contam Toxicol 25:271–278

    Article  CAS  Google Scholar 

  • Zhang WX, Bouwer EJ, Ball WP (1998) Bioavailability of hydrophobic organic contaminants: effects and implications of sorption-related mass transfer on bioremediation. Ground Water Monit Remediat 18:126–138

    Article  Google Scholar 

  • Zhao Y, Lazou K, Schelfaut M, De Reu L, Sandra P (2000) Determination of chlormequat residues in pears and pear concentrates by benchtop LC-ESI-MS. Chromatographia 51:531–535

    Article  CAS  Google Scholar 

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Acknowledgements

The project was supported financially by Copenhagen Energy (Københavns Energi A/S). We wish to thank P. Stockmarr (GEUS) for skilled technical assistance in connection with method development and sample analysis, P. Olsen (Aarhus University), L. Gudmundsson (GEUS), C. Andersen (Jyndevad Research Station), P. Boesen (Estrup Research Station) and J. Molbo (Silstrup Research Station) for assistance with the field leaching experiments, and D. I. Barry for linguistic assistance.

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  1. Trine Henriksen

    Present address: Department of Clinical Pharmacology, Department Q-7642, Rigshospitalet, Tagensvej 20, 2200, Copenhagen, Denmark

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  1. The Geological Survey of Denmark and Greenland (GEUS), Øster Voldgade 10, 1350, Copenhagen, Denmark

    René K. Juhler, Trine Henriksen, Annette E. Rosenbom & Jeanne Kjaer

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Juhler, R.K., Henriksen, T., Rosenbom, A.E. et al. Fate and transport of chlormequat in subsurface environments. Environ Sci Pollut Res 17, 1245–1256 (2010). https://doi.org/10.1007/s11356-010-0303-5

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