Detrimental Effects of Glyphosate on Nutritional Status of Plants with Micronutrients I. Cakmak Sabanci University Istanbul, Turkey cakmak@sabanciuniv.edu Glyphosate: extensively applied herbicide • Increasing usage in minimumand no-tillage agricultural practices • Extensive application on RR crops . In regions with extensive use of glyphosate there are increasing reports on: • reductions in growth and yield, • increases in disease problems, • increased use of insecticides and fungicides, • inhibition of N fixing bacteria • increased use of foliar micronutrient fertilizers • micronutrient deficiencies Particular micronutrient deficiencies induced by Glyphosate: Manganese and Iron Deficiencies Repeated use of glyphosate induces Fe and Mn deficiencies in soybeans in USA (Photo: Prof. Don Huber) (areas which are not treated with glyphosate) Glyphosate-induced Fe-deficiency chlorosis + gyphosate + seed Fe treatment + gyphosate – seed Fe treatment - gyphosate + seed Fe treatment Photo: N.C. Hansen, Fort Collins, USA (Jolley et al., Soil Sci Plant Nutr. 50, 793-981, 2004) Interaction of seed applied Fe and glyphosate application on Fe deficiency chlorosis in soybeans; Minnesota, USA visual chlorosis scrore Treatment (1=green to 5 =severe) – Fe Control grain yield + Fe* (t/ha) – Fe 3.1 2.8 1.01 3.7 3.3 0.27 + Fe* 1.70 (no herbicide) Glyphosate 0.61 * 50g Fe/ha as FeEDDHA applied to seeds (Jolley et al., Soil Sci Plant Nutr. 50, 793-981, 2004) Foliar and Soluble Micronutrient* Sales in USA RoundUp Ready Corn, Soy 5000 4500 4000 3500 3000 2000 2001 2002 2003 2004 2500 2000 1500 1000 (*represents 500 approx 30% of US Sales) 0 B Cu Fe Mn Zn (Courtesy of Prof. P. Brown, UC Davis) Glyphosate is toxic to plants whether from a drift or residues in soil A significant amount of glyphosate applied to target plants reaches the soil as a result of direct contact, wash off from leaves and exudation from roots of the treated weeds. Up to 10 % of the applied glyphosate move to non-target plants entweb.clemson.edu. http://www.uky.edu/Ag/Tobacco/Pages/RoundupFloat.html no Glyphosate with Glyphosate REMEMBER Glyphosate is highly phloem mobile Application of glyphosate on target plants (weeds)/glyphosate resistant cultivars; very quick uptake by leaves. Rapid translocation of glyphosate from shoot to root Release of glyphosate into the rhizosphere Adaptive Root Responses of Strategy-I Plants to Fe Deficiency Rhizosphere/Soil FeIII Chelator Apoplasm Plasma Membrane TR FeIII Chelate FeIII Cytoplasm FeII R FeIII H+ FeIII PUMP H+ Reductants (Chelators) Marschner and Römheld, 1995; Plant and Soil R: Ferric Reductase R Effect of iron deficiency in cucumber on pH decreasing and reducing capacity of the roots +Fe -Fe +Fe -Fe Romheld et al., 1981 Effect of Glyphosate on Ferric Reductase Time dependent inhibition of ferric reductase activity Fe reduction capacity -1 -1 (µmol Fe(II) g root dry wt 3 h ) in Fe-deficient sunflower plants (+Glyp: 1.89 mM glyphosate or 6% of the recommended rate for weed control) 80 Fe deficient LSD0.05 60 40 Control (+Fe) 20 0 -Glyp. Ozturk et al., 2007 +Glyp. 6h +Glyp. 12h +Glyp. 24h -Glyp. +Fe Fe reduction capacity -1 -1 (µmol Fe(II) g root dry wt 3 h ) Dose dependent inhibition of ferric reductase activity by glyphosate (+Glyp: 0.32, 0.95 and 1.89 mM Fe deficient 80 60 LSD0.05 40 Control (+Fe) 20 0 -Glyp. Ozturk et al., 2007 +Glyp. +Glyp. +Glyp. 0.32 mM 0.95 mM 1.89 mM -Glyp. +Fe Foliar applications of glyphosate (Glyp) at 0.32 mM, 0.95 mM and 1.89 mM for 24h. Staining of Ferric Reductase Activity GLYPHOSATE Ozturk et al., 2007 Fe Deficient Plants Effect of foliar applied of glyphosate (1.89 mM ) for 24h on ferric reductase activity. -Fe -Fe +Glyp (1.89 mM) Ozturk et al., 2007 -G lyp . +F e 12 +G ly p . -G l +G 0 yp ly .32 . p. m +G 0 M . 9 ly p. 5 m 1. M 89 m M (µmol g -1 FW) Shikimate accumulation Dose Dependent Shikimate Accumulation 15 Shoot 9 6 3 0 Ozturk et al., 2007 lyp -G l +G . 0. yp. lyp 32 m . M +G 0. 9 lyp 5 . 1 mM .8 9 m M -G ly p. +F e +G (µmol g -1 FW) Shikimate accumulation Dose Dependent Shikimate Accumulation 8 6 Root 4 2 0 Ozturk et al., 2007 15 Shoot 0 -G +G l yp lyp . +G . 6 lyp h +G . 12 lyp h .2 4h -G ly p. +F e -G ly p. +F e 12 -G +G l yp lyp . +G . 6 lyp h +G . 12 lyp h .2 4h (µmol g -1 FW) Shikimate accumulation Time Dependent Shikimate Accumulation 8 Root 6 9 4 6 2 3 0 Ozturk et al., 2007 Short-Term Experiments: Glyphosate inhibits root uptake and root-to-shoot transport of micronutrients ROOT UPTAKE TRANSLOCATION TO SHOOT Root Uptake 59 800 Fe LSD0.05=108 600 Translocation 59Fe 25 59 20 LSD0.05=7.0 Fe 15 400 -1 Root uptake rate (nmol g root dry wt 4 h ) 0 54 Mn 1200 LSD0.05=22.5 -1 900 54Mn 600 300 0 65 3000 Zn LSD0.05= ns 2250 65Zn Shoot translocation rate (nmol g-1 root dry wt 4 h-1) 10 200 5 0 LSD0.05=3.6 75 50 25 0 65 Zn 100 LSD0.05= ns 75 50 750 25 0 0 Glyphosate Mn 100 1500 Control 54 125 Control Effect of 1.89 mM glyphosate (equivalent to 6 % of the recommended dosage for weed control in the field) on root uptake and shoot translocation of 59Fe, 54Mn and 65Zn in sunflower plants. Glyphosate Eker et al., 2006: J. Agric. Food Chem. 26, 10019 -10025 Adaptive Root Responses to Iron and Zinc Deficiencies in Cereals Rhizosphere/Soil Apoplasm Plasma Membrane Cytoplasm PHYTOSIDEROPHORES FeIII ZnII FeIII FeIII-PS TR ZnII ZnII-PS TR: Transporter Protein Marschner and Römheld, 1995; Plant and Soil FeIII-PS ZnII-PS Mugineic Acid Family Biosynthetic Pathway of Mugineic Acid Family Mori et al., 1990 Phytosiderophores Fe OH Fe NH2 Fe3+-Deoxymugineic acid Fe3+-Nicotianamine Similar Stereochemical Structure between Fe3+-DMA and Fe3+-NA Mori, et al, 1990 Phytosiderophore Release from Roots Phytosiderophore release -1 -1 (nmol PS plant 3h ) 160 +Fe -Fe, 0% Glyp -Fe, 1% Glyp -Fe, 3% Glyp -Fe, 9% Glyp 120 80 40 0 +Fe -Fe Ozturk et al., 2008 Phytosiderophore Release from Wheat Roots Phytosiderophore release -1 -1 (nmol PS plant 3h ) 160 120 80 +Fe -Fe, 0% Glyp -Fe, 1% Glyp -Fe, 3% Glyp -Fe, 9% Glyp 40 0 Ozturk et al., 2008 Glyphosate Applicaton Mobilization of Zn from Calcareous Soil by Phytosiderophores Control (+Fe, -Glyp) -Fe, -Glyp -Fe, 1% Glyp -Fe, 3% Glyp -Fe, 9% Glyp 0.3 -1 Mobilized Zn (µg g soil) Mobilized Zn, µg -1 soil 0.4 0.2 0.1 0.0 Ozturk et al., 2008 Glyphosate Application Mobilization of Mn from Calcareous Soil by Phytosiderophores Mobilized Mn, µg -1 soil Control (+Fe, -Glyp) -Fe, -Glyp -Fe, 1% Glyp -Fe, 3% Glyp -Fe, 9% Glyp 0.2 0.1 0.0 Ozturk et al., 2008 Glyphosate Application REMEMBER Glyphosate is highly phloem mobile Application of glyphosate on target plants (weeds)/glyphosate resistant cultivars; very quick uptake by leaves. Rapid translocation of glyphosate from shoot to root Release of glyphosate into the rhizosphere Glyphosate applied to target plants is released into the rhizosphere Induction of Fe deficiency chlorosis in non-target plants (sunflower) Soybean Target Sunflower Indicator Soybean Target Sunflower Indicator Soybean Target Soybean Target (Neumann et al., 2005, J. Plant Dis. Prot.) Glyphosate application to target plants (soybean) Development of Fe deficiency symptoms in non-target plants … Glyphosate released in the rhizosphere reduces Mn uptake 54Mn in shoots Inhibited Mn acquisition by non-target plants (sunflower) grown in nutrient solution together with glyphosate treated target plants (soybean) for 2, 4 and 6 days. Neumann et al., 2005, J. Plant Dis. Prot. Significantly lower Mn uptake/accumulation in RR-soybeans leaf tissue Mn, ppm 120 KS 4202 100 KS 4202 RR 80 KS 4202 KS 4202R 60 40 20 0 2,5 5 7,5 Mn-rate, lb/a (B.Gordon, 2006; Kansas State Univ.) Inhibition of MnO2 Reduction in Soil-filled Rhizoboxes after Glyphosate Treatment to Target Plants (soybean) Control + Glyphosate MnO2 Reduction in Soil-filled Rhizobox Culture of sunflower (non-target) and RR-Soybean with and without foliar Glyphosate spray (Neumann et al., 2005) Glyphosate Reduces Grain Mn, Mg and Ca 0 0.3 0.6 Glyphosate Application, % 0.9 Grain, straw and whole plant dry matter yield as Dry matter yield, g plant-1 affected by drift rates of glyphosate in soybean 8.0 Grain 12 Straw 20 10 16 6.0 8 4.0 Whole plant 12 6 8 4 2.0 0.0 control 0.3 0.3 Control 0.6 0.6 0.9 0.9 2 4 0 0 control 0.3 0.3 Control 0.6 0.6 0.9 0.9 control 0.3 0.3 Control 0.6 0.6 0.9 0.9 Glyphosate treatment, % of recommended Yazici et al., 2008 Glyphosate Applied: 3 Times; one before flowering and 2flowering times after flowering Glyphosate applied 3 times before 1.8 0.30 0.5 Mg K K 1.5 Ca Mg 0.25 Ca 0.4 % Grain concentration, Grain concentration of K, Mg and Ca as affected by drift rates of glyphosate in soybean 1.2 0.20 0.9 0.15 0.6 0.10 0.3 control 0 0.3 0.6 0.9 0.3 0.6 0.9 0.2 control 0 0.3 0.6 0.6 0.9 0.9 0.3 control 0 0.3 0.6 0.9 0.3 0.6 0.9 Glyphosate treatment, % of recommended Glyphosate treatment, % of recommended Yazici et al., 2008 Grain concentration, mg kg-1 Grain concentration of Fe, Mn and Zn as affected by drift rates of glyphosate in soybean 100 80 90 Fe 80 Fe 70 60 Mn Mn Zn 50 Zn 60 70 40 60 50 50 30 40 40 30 30 0 0.3 control 0.3 0.6 0.6 0.9 0.9 20 control 0.3 0 0.3 0.6 0.9 0.9 0.6 0 0.30.3 control 0.60.6 0.9 0.9 Glyphosate treatment, % of recommended Yazici et al., 2008 Seed Mn and Ca very important for seed viability and seedling vigour Dry matter yield of young and old leaves of soybean plants as affected by drift rates of glyphosate Young leaves Dry matter yield, g plant-1 140 Old leaves 800 120 600 100 80 400 60 40 200 20 0 0 0 control 0.3 0.3 0.6 0.6 0.9 0.9 control 0 0.3 0.3 0.6 0.6 0.9 0.9 Glyphosate treatment, % of recommended Yazici et al., 2008 Leaf concentration, % Concentration of K, Mg and Ca in soybean leaves as affected by drift rates of glyphosate 0.7 3.5 K 3.0 1.8 0.6 Mg Ca 1.5 0.5 1.2 2.5 0.4 2.0 0.9 0.3 1.5 0.2 control 0 0.3 0.6 0.9 0.3 0.6 0.9 0.6 control 0 0.3 0.6 0.9 0.3 0.6 0.9 control 0 0.3 0.6 0.9 0.3 0.6 0.9 Glyphosate treatment, % of recommended Hande et al., 2008 Plants with low Mg are highly sensitive to glyphosate Hande et al., 2008 Plants with low Mg are highly sensitive to glyphosate Hande et al., 2008 What is the effect of Glyphosate?? Effectiveness of Glyphosate Effect of Glyphosate with and without calcium in the tank Control Glyphosate Glyphosate + Calcium Glyphosate binds with the cations to form a strong complex which is not bio-available. Only unbound glyphosate act as a herbicide. www.loveland.co.uk/ Gifs/X-Change-du-pont.gif Glyphosate binds with the cations to form a strong complex which is not bioavailable. Only unbound glyphosate act as a herbicide. Conclusions • Routine glyphosate use in agricultural systems results in considerable side effects on plant growth and mineral nutrition of plants • Glyphosate is antagonistic to the uptake, transport and accumulation (tissue concentration) of Fe,Mn, Ca and Mg possibly due to the formation of poorly soluble glyphosate-metal complexes (??) Conclusions-cont • Glyphosate impairs genetic adaptation mechanisms of plants to Fe deficiency • Plants grown under low Mg are very sensitive to glyphosate • A new risk assessment for glyphosate is urgently needed, Root Tips: Co-localization of Ferric Reductase and Glyphosate Accumulation Leading 10 Health Risk Factors in Developing Countries, % Cause of Disease Burden Underweight 14.9% Unsafe sex 10.2% Unsafe water 5.5% Indoor smoke 3.7% Zinc Deficiency 3.2% WHO, 2002 Iron deficiency 3.1% Vitamin A def. Blood pressure Tobacco Cholesterol 3.0% 2.5% 2.0% 1.9% Copenhagen Consensus-2004 Worldwide Panel of Distinguished Economists including Nobel Prize-Winners Top Four Global Challenges • Control of HIV/AIDS • Providing micronutrients (Fe, Zn..) to human populations • Trade Liberalization • Control of Malaria Source:: http://www.copenhagenconsensus.com) Interference of glyphosate with root uptake and transport of micronutrients may also represent a potential threat to human nutrition and human health L. Ozturk Sabanci University G. Neumann T. Tesfamariam Fanghua Ye C. Weishaar K. Stock-de Oliveira Souza E. Landsberg S. Kohls University Hohenheim (U.H.) V. Römheld (S. Bott: Uni.Hohenheim) T. Yamada I. Cakmak Obrigado… Sabanci University Shoot and root dry matter production and chlorophyll level as influenced from glyphosate application for 24 h -Fe -Glyp. +Glyp. 0.32 mM +Glyp. 0.95 mM +Glyp. 1.89 mM Dry matter production Shoot Root (mg plant-1) 208 ± 16 58 ± 8 202 ± 16 55 ± 8 208 ± 15 56 ± 11 194 ± 23 53 ± 9 Chloropyll (SPAD) 21.2 ± 1.0 21.3 ± 0.7 21.7 ± 1.4 21.8 ± 2.3 +Fe -Glyp. 226 ± 30 39.2 ± 1.9 Treatments LSD0.05 24 61 ± 13 12 Ozturk et al., 2007 2.3 +G ly +G ly +G ly 1. 89 0. 95 0. 32 -G lyp p p p +F e m M m M m M -G lyp Total carbohydrates (mg glucose equiv. g-1 FW) Carbohydrates in Apical Parts of Roots 15 + Glyphosate 12 9 6 3 0 Ozturk et al., 2007 Root Responses to Fe Deficiency in Strategy-I Plants Rhizosphere FeIII Chelator Apoplasm Plasma Membrane TR FeIII Chelate FeIII Cytoplasm FeII NAD(P)H R FeIII NAD(P)+ H+ FeIII PUMP H+ Reductants (Chelators) Marschner and Römheld, 1995; Plant and Soil R: Ferric Reductase R 1. 89 0. 95 0. 32 -G lyp p p p +F e m M m M m M 40 +G ly +G ly +G ly -G lyp NADPH oxidation (nmol min-1 g-1 FW) Capacity of Roots to Oxidize NADPH + Glyphosate 30 20 10 0 Ozturk et al., 2007 Close Relationship between Fe Deficiency Tolerance and Ferric Reductase Activity in Soybean Soybean Genotypes Marschner and Romheld, 1995 Release of chelating compounds (µmol Fe equiv. g-1 fresh wt. h-1) Release of Phytosiderophores from Roots Correlate with Tolerance Fe Deficiency Chlorosis 60 50 +Fe -Fe 40 30 20 10 0 rice sorghum maize oat Wheat Chlorosis resistance (Römheld & Marschner (1986): Adv. in Plant Nutr 2, 155-204)