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Herbicides in river water across the northeastern Italy: occurrence and spatial patterns of glyphosate, aminomethylphosphonic acid, and glufosinate ammonium

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Abstract

Glyphosate and glufosinate ammonium are the active ingredients of commonly used herbicides. Active agricultural lands extend over a large part of the Veneto region (Eastern Po Valley, Italy) and glyphosate and glufosinate ammonium are widely used. Consequently, surface waters can be potentially contaminated. This study investigates the occurrence of glyphosate and glufosinate ammonium as well as aminomethylphosphonic acid (AMPA, the degradation product of glyphosate) in river water of Veneto. Eighty-six samples were collected in 2015 at multiple sampling points across the region. Samples were analyzed for the two target herbicides, AMPA as well as for other variables, including water temperature, pH, dissolved oxygen, conductivity, hardness, BOD, COD, inorganic ions, total nitrogen, total phosphorus, total suspended solids, arsenic, and lead. The average concentrations (all samples) were 0.17, 0.18, and 0.10 μg L−1 for glyphosate, AMPA, and glufosinate ammonium, respectively. The European upper tolerable level for pesticides (annual average 0.1 μg L−1) was often exceeded. Chemometric analysis was therefore applied to (i) investigate the relationships among water pollutants, (ii) detect the potential sources of water contamination, (iii) assess the effective water pollution of rivers by identifying river basins with anomalous pollution levels, and (iv) assess the spatial variability of detected sources. Factor analysis identified four factors interpreted as potential sources and processes (use of herbicides, leaching of fertilizers, urban/industrial discharges, and the biological activity on polluted or stagnant waters). A discriminant analysis revealed that the pollution from anthropogenic discharges is homogeneously present in surface water of Veneto, while biological activity and fertilizers present heterogeneous distributions. This study gives insights into the concentrations of herbicides in rivers flowing through a wide region that has heavy use of these chemicals in agriculture. The study also points out some hot-spots and suggests the future implementation of the current monitoring protocols and network.

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References

  • Aparicio VC, De Gerónimo E, Marino D, Primost J, Carriquiriborde P, Costa JL (2013) Environmental fate of glyphosate and aminomethylphosphonic acid in surface waters and soil of agricultural basins. Chemosphere 93(9):1866–1873

    Article  CAS  Google Scholar 

  • APPA (2014) Elaborazione dei dati di vendita dei prodotti fitosanitari dal 2002 al 2012. http://www.appa.provincia.tn.it/fitofarmaci/programmazione_dei_controlli_ambientali/-Criteri_vendita_prodotti_fitosanitari/pagina55.html [in Italian]

  • ARPAV (2017) Rapporto sulla risorsa idrica del Veneto [Report on water resources of the Veneto]. http://www.arpavenetoit/temi-ambientali/idrologia/file-e-allegati/rapporti-e-documenti/idrologia-regionale/idrologia-regionale-rapporti-sulla-risorsa-idrica/2015/rapporti-risorsa-idrica-2015. Accessed Mar 2017 [in Italian]

  • Battaglin WA, Kolpin DW, Scribner EA, Kuivila KM, Sandstrom MW (2005) Glyphosate, other herbicides, and transformation products in midwestern streams: 2002. J Am Water Resour As 41(2):323–332

    Article  CAS  Google Scholar 

  • Battaglin WA, Rice KC, Focazio MJ, Salmons S, Barry RX (2009) The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming: 2005–2006. Environ Monit Assess 155(1–4):281–307

    Article  CAS  Google Scholar 

  • Battaglin, WA, Meyer, MT, Kuivila, KM and Dietze, JE:2014a Glyphosate and its degradation product AMPA occur frequently and widely in US soils, surface water, groundwater, and precipitation. J Am Water Resour As 50(2):275–290

  • Battaglin WA, Meyer MT, Kuivila K, Dietze JE (2014b) Glyphosate and AMPA in US streams, groundwater, precipitation and soils. J Am Water Resour Assoc 50(2):275–290

    Article  CAS  Google Scholar 

  • Baylis AD (2000) Why glyphosate is a global herbicide: strengths, weaknesses and prospects. Pest Manag Sci 56:299–308

    Article  CAS  Google Scholar 

  • Bergstrom L, Borjesson E, Stenstrom J (2011) Laboratory and lysimeter studies of glyphosate and aminomethylphosphonic acid in a sand and a clay soil. J Environ Qual 40:98–108

    Article  CAS  Google Scholar 

  • Bøhn T, Cuhra M, Traavik T, Sanden M, Fagan J, Primicerio R (2014) Compositional differences in soybeans on the market: glyphosate accumulates in Roundup Ready GM soybeans. Food Chem 153:207–215

    Article  CAS  Google Scholar 

  • Borggaard OK, Gimsing AL (2008) Fate of glyphosate in soil and the possibility of leaching to ground and surface waters: a review. Pest Manag Sci 64(4):441–456

    Article  CAS  Google Scholar 

  • Box GEP, Cox DR (1964) An analysis of transformations. J Roy Statist Soc B 26:211–252

    Google Scholar 

  • Calas AG, Richard O, Même S, Beloeil JC, Doan BT, Gefflaut T, Même W, Crusio WE, Pichon J, Montécot C (2008) Chronic exposure to glufosinate-ammonium induces spatial memory impairments, hippocampal MRI modifications and glutamine synthetase activation in mice. Neurotoxicology 29(4):740–747

    Article  CAS  Google Scholar 

  • Capraro F, Bizzotto A, Masiol M, Pavoni B (2011) Chemical analyses of spring waters and factor analysis to monitor the functioning of a karstic system. The role of precipitations regimen and anthropic pressures. J Environ Monit 13:2543–2549

    Article  CAS  Google Scholar 

  • Carey RO, Migliaccio KW (2009) Contribution of wastewater treatment plant effluents to nutrient dynamics in aquatic systems: a review. Environ Manag 44(2):205–217

    Article  Google Scholar 

  • Carraro A, Fabbri P, Giaretta A, Peruzzo L, Tateo F, Tellini F (2013) Arsenic anomalies in shallow Venetian Plain (Northeast Italy) groundwater. Environ Earth Sci 70(7):3067–3084

    Article  Google Scholar 

  • Carraro A, Fabbri P, Giaretta A, Peruzzo L, Tateo F, Tellini F (2015) Effects of redox conditions on the control of arsenic mobility in shallow alluvial aquifers on the Venetian Plain (Italy). Sci Total Environ 532:581–594

    Article  CAS  Google Scholar 

  • Carpenter D, Boutin C (2010) Sublethal effects of the herbicide glufosinate ammonium on crops and wild plants: short-term effects compared to vegetative recovery and plant reproduction. Ecotoxicology 19(7):1322–1336

    Article  CAS  Google Scholar 

  • Cerdeira AL, Duke SO (2006) The current status and environmental impacts of glyphosate-resistant crops: a review. J Environ Qual 35:1633–1658

    Article  CAS  Google Scholar 

  • Cherry KA, Shepherd M, Withers PJA, Mooney SJ (2008) Assessing the effectiveness of actions to mitigate nutrient loss from agriculture: a review of methods. Sci Total Environ 406(1):1–23

    Article  CAS  Google Scholar 

  • Coupe RH, Kalkhoff SJ, Capel PD, Gregoire C (2012) Fate and transport of glyphosate and aminomethylphosphonic acid in surface waters of agricultural basins. Pest Manag Sci 68(1):16–30

    Article  CAS  Google Scholar 

  • Crowe AS, Leclerc N, Struger J, Brown S (2011) Application of a glyphosate-based herbicide to phragmites australis: impact on groundwater and near-shore lake water at a beach on Georgian Bay. J Great Lakes Res 37(4):616–624

    Article  CAS  Google Scholar 

  • Dinehart SK, Smith LM, McMurry ST, Anderson TA, Smith PN, Haukos DA (2009) Toxicity of a glufosinate-and several glyphosate-based herbicides to juvenile amphibians from the southern High Plains, USA. Sci Total Environ 407(3):1065–1071

    Article  CAS  Google Scholar 

  • Duke SO, Powles SB (2008) Glyphosate: a once-in-a-century herbicide. Pest Manag Sci 64(4):319–325

    Article  CAS  Google Scholar 

  • Duke SO (2014) Biotechnology: herbicide-resistant crops. In: Van Alfen NK (ed) Encyclopedia of Agriculture and Food Systems, vol 2nd. Elsevier, Amsterdam, pp 94–116

    Chapter  Google Scholar 

  • EC (European Commission) (1998) Directive 1998/83/EC of 3 November 1998 on the quality of water intended for human consumption. Official J Europ Comm 5(98):L330

    Google Scholar 

  • EC (European Commission) (2000) Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy. Official J Europ Union L 327 :22/12/2000 P 0001–0073

  • EEA (Eur Environ Agency) (2017) CORINE Land Cover Database 2012. http://land.copernicus.eu/pan-european/corine-land-cover/clc-2012. Accessed Nov 2017

  • Facca C, Pellegrino N, Ceoldo S, Tibaldo M, Sfriso A (2011) Trophic conditions in the waters of the Venice lagoon (northern Adriatic Sea, Italy). Open Oceanogr J 5:1–13

    Article  CAS  Google Scholar 

  • Giandon P, Vinci I, Fantinato L (2000) Heavy metal concentration in the soils of the basin draining the Venice lagoon. Boll Soc Ital Sci Suolo 49(1–2):359–366 [in Italian]

    Google Scholar 

  • Giandon P, Cappellin R, Ragazzi F, Vinci I (2004) Confronto tra il livello naturale e il livello antropico dei metalli pesanti nei suoli della pianura veneta in relazione al materiale di partenza. Bollettino della Società Italiana di Scienza del Suolo 53(1–2):540–544 [in Italian]

    Google Scholar 

  • Glozier NE, Struger J, Cessna AJ, Gledhill M, Rondeau M, Ernst WR, Sekela MA, Cagampan SJ, Sverko E, Murphy C, Murray JL (2012) Occurrence of glyphosate and acidic herbicides in select urban rivers and streams in Canada (2007). Environ Sci Pollut Res 19(3):821–834

    Article  CAS  Google Scholar 

  • Giesy JP, Dobson S, Solomon KR (2000) Ecotoxicological risk assessment for Roundup® herbicide. Rev Environ Contam Toxicol 167:35–120

    CAS  Google Scholar 

  • Hanke I, Singer H, Hollender J (2008) Ultratrace-level determination of glyphosate, aminomethylphosphonic acid and glufosinate in natural waters by solid-phase extraction followed by liquid chromatography–tandem mass spectrometry: performance tuning of derivatization, enrichment and detection. Anal Bioanal Chem 391(6):2265–2276

    Article  CAS  Google Scholar 

  • Hanke I, Wittmer I, Bischofberger S, Stamm C, Singer H (2010) Relevance of urban glyphosate use for surface water quality. Chemosphere 81:422–429

    Article  CAS  Google Scholar 

  • Hayton JC, Allen DG, Scarpello V (2004) Factor retention decisions in exploratory factor analysis: a tutorial on parallel analysis. Organ Res Methods 7(2):191–205

    Article  Google Scholar 

  • Hering D, Borja A, Carstensen J, Carvalho L, Elliott M, Feld CK, Heiskanen AS, Johnson RK, Moe J, Pont D, Solheim AL (2010) The European water framework directive at the age of 10: a critical review of the achievements with recommendations for the future. Sci Total Environ 408(19):4007–4019

    Article  CAS  Google Scholar 

  • ISO (2014) Water quality—determination of glyphosate and AMPA—method using high performance liquid chromatography (HPLC) with tandem mass spectrometric detection. http://www.isoorg/iso/catalogue_detailhtm?csnumber=56140. Accessed Feb 2017

  • IUPAC (International Union of Pure Appl Chem) (2014). Compendium of chemical terminology—Gold Book Version 2.3.3. http://goldbook.iupac.org. Accessed Apr 2018

  • Jaworska J, Van Genderen-Takken H, Hanstveit A, van de Plassche E, Feijtel T (2002) Environmental risk assessment of phosphonates, used in domestic laundry and cleaning agents in the Netherlands. Chemosphere 47(6):655–665

    Article  CAS  Google Scholar 

  • Khan MB, Masiol M, Hofer A, Pavoni B (2014) Harmful elements in estuarine and coastal systems. In: PHEs, environment and human health. Springer, The Netherlands, pp 37–83

    Chapter  Google Scholar 

  • Laitinen P, Siimes K, Eronen L, Rämö S, Welling L, Oinonen S, Rämö S, Welling L, Oinonen S, Mattsoff L, Ruohonen-Lehto M (2006) Fate of the herbicides glyphosate, glufosinateammonium, phenmedipham, ethofumesate and metamitron in two Finnish arable soils. Pest Manag Sci 62:473–491

    Article  CAS  Google Scholar 

  • Lajmanovich RC, Cabagna-Zenklusen MC, Attademo AM, Junges CM, Peltzer PM, Bassó A, Lorenzatti E (2014) Induction of micronuclei and nuclear abnormalities in tadpoles of the common toad (Rhinella arenarum) treated with the herbicides Liberty® and glufosinate-ammonium. Mutat Res Genet Toxicol Environ Mutagen 769:7–12

    Article  CAS  Google Scholar 

  • Lapworth DJ, Baran N, Stuart ME, Ward RS (2012) Emerging organic contaminants in groundwater: a review of sources, fate and occurrence. Environ Pollut 163:287–303

    Article  CAS  Google Scholar 

  • LGC Aquacheck (2017) Standards Proficiency Testing PT AQ492 LGC Standards Proficiency Testing, Bury, Lancashire, UK. https://us.lgcstandards.com/US/en/proficiency-testing. Accessed Nov 2017

  • Lesueur C, Pfeffer M, Fuerhacker M (2005) Photodegradation of phosphonates in water. Chemosphere 59(5):685–691

    Article  CAS  Google Scholar 

  • Mahler BJ, Van Metre PC, Burley TE, Loftin KA, Meyer MT, Nowell LH (2016) Similarities and differences in occurrence and temporal fluctuations in glyphosate and atrazine in small Midwestern streams (USA) during the 2013 growing season. Sci Total Environ 579:149–158

    Article  CAS  Google Scholar 

  • Masiol M, Facca C, Visin F, Sfriso A, Pavoni B (2014) Interannual heavy element and nutrient concentration trends in the top sediments of Venice lagoon (Italy). Mar Pollut Bull 89(1):49–58

    Article  CAS  Google Scholar 

  • Mao YC, Hung DZ, Wu ML, Tsai WJ, Wang LM, Ger J, Deng JF, Yang CC (2012) Acute human glufosinate-containing herbicide poisoning. Clin Toxicol 50(5):396–402

    Article  CAS  Google Scholar 

  • Meffe R, de Bustamante I (2014) Emerging organic contaminants in surface water and groundwater: a first overview of the situation in Italy. Sci Total Environ 481:280–295

    Article  CAS  Google Scholar 

  • Moore, JW, Ramamoorthy, S (2012) Heavy metals in natural waters: applied monitoring and impact assessment. Springer Science & Business Media

  • Morrissey CA, Mineau P, Devries JH, Sanchez-Bayo F, Liess M, Cavallaro MC, Liber K (2015) Neonicotinoid contamination of global surface waters and associated risk to aquatic invertebrates: a review. Environ Int 74:291–303

    Article  CAS  Google Scholar 

  • Nowack B (2003) Environmental chemistry of phosphonates. Water Res 37(11):2533–2546

    Article  CAS  Google Scholar 

  • Peltzer PM, Junges CM, Attademo AM, Bassó A, Grenón P, Lajmanovich RC (2013) Cholinesterase activities and behavioral changes in Hypsiboas pulchellus (Anura: Hylidae) tadpoles exposed to glufosinate ammonium herbicide. Ecotoxicology 22(7):1165–1173

    Article  CAS  Google Scholar 

  • Poiger T, Buerge IJ, Bächli A, Müller MD, Balmer ME (2017) Occurrence of the herbicide glyphosate and its metabolite AMPA in surface waters in Switzerland determined with on-line solid phase extraction LC-MS/MS. Environ Sci Pollut Res 24(2):1588–1596

    Article  CAS  Google Scholar 

  • Reimann C, Filzmoser P, Garrett RG (2002) Factor analysis applied to regional geochemical data: problems and possibilities. Appl Geochem 17(3):185–206

    Article  CAS  Google Scholar 

  • Richardson SD, Kimura SY (2015) Water analysis: emerging contaminants and current issues. Anal Chem 88(1):546–582

    Article  CAS  Google Scholar 

  • Schinegger R, Trautwein C, Melcher A, Schmutz S (2012) Multiple human pressures and their spatial patterns in European running waters. Water Environ J 26(2):261–273

    Article  Google Scholar 

  • Scribner, EA, Battaglin, WA, Gilliom, RJ, Meyer, MT (2007) Concentrations of glyphosate, its degradation product, aminomethylphosphonic acid, and glufosinate in ground-and surface-water, rainfall, and soil samples collected in the United States: 2001–06 (No 2007-5122), Geological Survey (US)

  • Skark C, Zullei-Seibert N, Schöttler U, Schlett C (1998) The occurrence of glyphosate in surface water. Int J Environ Anal Chem 70(1–4):93–104

    Article  CAS  Google Scholar 

  • Siimes K, Rämö S, Welling L, Nikunen U, Laitinen P (2006) Comparison of the behaviour of three herbicides in a field experiment under bare soil conditions. Agric Water Manag 84(1):53–64

    Article  Google Scholar 

  • Smedley PL, Kinniburgh DG (2002) A review of the source, behaviour and distribution of arsenic in natural waters. Appl Geochem 17(5):517–568

    Article  CAS  Google Scholar 

  • Sørensen SR, Schultz A, Jacobsen OS, Aamand J (2006) Sorption, desorption and mineralisation of the herbicides glyphosate and MCPA in samples from two Danish soil and subsurface profiles. Environ Pollut 141:184–194

    Article  CAS  Google Scholar 

  • Stuart M, Lapworth D, Crane E, Hart A (2012) Review of risk from potential emerging contaminants in UK groundwater. Sci Total Environ 416:1–21

    Article  CAS  Google Scholar 

  • Struger J, Van Stempvoort DR, Brown SJ (2015) Sources of aminomethylphosphonic acid (AMPA) in urban and rural catchments in Ontario, Canada: glyphosate or phosphonates in wastewater? Environ Pollut 204:289–297

    Article  CAS  Google Scholar 

  • Todorovic GR, Rampazzo N, Mentler A, Blum WE, Eder A, Strauss P (2014) Influence of soil tillage and erosion on the dispersion of glyphosate and aminomethylphosphonic acid in agricultural soils. Int Agrophys 28(1):93–100

    Article  CAS  Google Scholar 

  • Tukey J (1949) Comparing individual means in the analysis of variance. Biometrics 5(2):99–114

    Article  CAS  Google Scholar 

  • Ungaro F, Ragazzi F, Cappellin R, Giandon P (2008) Arsenic concentration in the soils of the Brenta Plain (northern Italy): mapping the probability of exceeding contamination thresholds. J Geochem Expl 96(2):117–131

    Article  CAS  Google Scholar 

  • US Geological Survey (2011) Change to solubility equations for oxygen in water: office of water quality technical memorandum 201103. https://water.usgs.gov/admin/memo/QW/qw1103pdf. Accessed Nov 2017

  • Van Stempvoort DR, Roy JW, Brown SJ, Bickerton G (2014) Residues of the herbicide glyphosate in riparian groundwater in urban catchments. Chemosphere 95:455–463

    Article  CAS  Google Scholar 

  • Vera MS, Lagomarsino L, Sylvester M, Pérez GL, Rodríguez P, Mugni H, Sinistro R, Ferraro M, Bonetto C, Zagarese H, Pizarro H (2010) New evidences of Roundup® (glyphosate formulation) impact on the periphyton community and the water quality of freshwater ecosystems. Ecotoxicology 19(4):710–721

    Article  CAS  Google Scholar 

  • Withers PJA, Jarvie HP (2008) Delivery and cycling of phosphorus in rivers: a review. Sci Total Environ 400(1):379–395

    Article  CAS  Google Scholar 

  • Zareitalabad P, Siemens J, Hamer M, Amelung W (2013) Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in surface waters, sediments, soils and wastewater—a review on concentrations and distribution coefficients. Chemosphere 91(6):725–732

    Article  CAS  Google Scholar 

  • Zirino A, Elwany H, Facca C, Neira C, Mendoza G (2016) Nitrogen to phosphorus ratio in the Venice (Italy) lagoon (2001–2010) and its relation to macroalgae. Mar Chem 180:33–41

    Article  CAS  Google Scholar 

  • Zonta R, Botter M, Cassin D, Pini R, Scattolin M, Zaggia L (2007) Sediment chemical contamination of a shallow water area close to the industrial zone of Porto Marghera (Venice lagoon, Italy). Mar Pollut Bull 55(10–12):529–542

    Article  CAS  Google Scholar 

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The authors gratefully acknowledge ARPAV for providing the data.

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Masiol, M., Giannì, B. & Prete, M. Herbicides in river water across the northeastern Italy: occurrence and spatial patterns of glyphosate, aminomethylphosphonic acid, and glufosinate ammonium. Environ Sci Pollut Res 25, 24368–24378 (2018). https://doi.org/10.1007/s11356-018-2511-3

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