Uptake and translocation of non-ionised pollutants by plants

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1 Uptake and translocation of non-ionised pollutants by plants Richard H. Bromilow Transfer of organic pollutants from soil to plants Reading University, September 25/26, 2007

2 Pesticides applied directly to the environment

3 Industrial pollutants escape directly or indirectly

4 Environmental behaviour of organic compounds influenced by physicochemical properties sorption to soil movement through soil bioaccumulation in organisms uptake and movement in plants atmospheric transport Metabolism and breakdown of organic pollutants determines their availability for long-term processes

5 Physicochemical properties of pesticides and organic pollutants The most important properties are:- Lipophilicity - assessed using the 1-octanol/water partition coefficient, K ow (expressed as log K ow or log P) Water solubility - strongly correlated with lipophilicity Vapour pressure can be important for lipophilic pesticides and pollutants in soil Acid/base strength - the pka is the ph at which a functional group is 50% ionised (eg -COOH, -NH 2 )

6 1-Octanol/water partition coefficients (K ow ) of classes of non-ionised pesticides and pollutants Insecticides Herbicides Fungicides Industrial pollutants Carbamates Organochlorines Organophosphates Pyrethroids Dinitroanilines Diphenyl ethers Thiocarbamates Triazines (-ones) Phenylureas/uracils Acylanilines Dicarboximides Sterol-biosynthesis inhibitors Chorinated solvents Nitrophenols Phthalates Polyaromatic hydrocarbons Polychlorinated biphenyls Polychlorinated dioxins/ benzofurans Log K ow polar lipophilic

7 Pathways of compound movement in soil are determined by the Henry Constant:- Henry constant = concentration in air concentration in water (calculated from the vapour pressure and water solubility)

8 Pathways of movement of organic compounds through soil as determined by Henry s constant Henry s constant (dimensionless) F12 (CCl 2 F 2 ) ethyl bromide carbon tetrachloride trichloroethylene dichloromethane tetrachlorobiphenyl TCDD DDT trifluralin pentachlorophenol dioctyl phthalate dibutyl phthalate dieldrin chlorpropham carbofuran monuron simazine bromacil Movement by diffusion in air Diffusion both in air and water Movement by diffusion only in the water phase hexazinone

9 Uptake and transport in barley of non-ionised [ 14 C]compounds applied via nutrient solution polar lipophilic intermediate

10 Long-distance transport of solutes in plants Xylem vessels - non-living tubes that carry water and nutrients from roots to shoots Phloem vessels - living tube-like cells without vacuoles that carry sugars and amino acids from leaf sources to sinks such as new growth

11 Cross-section of root showing the arrangement of cells and vascular tissues

12 Root Concentration Factor (RCF) = concentration in root concentration in nutrient solution

13 Relationship between the lipophilicity of non-ionised chemicals and their uptake by barley roots from nutrient solution Root Concentration Factor Mean uptake over 24 & 48 h Carbamoyloximes Phenylureas log (RCF-0.82) = 0.77log Kow Log Kow

14 Uptake of non-ionised pesticides by plant roots - conclusions Uptake is an equilibrium process that is rapidly attained Uptake occurs by both equilibration into the aqueous phase of roots and, more importantly for lipophilic compounds, by partitioning into the plant solids (eg lignin) The concentration factor is independent of uptake time, pesticide concentration and the solution ph

15 Transpiration Stream Concentration Factor (TSCF) = concentration in xylem sap concentration in nutrient solution = amount in plant shoot vol. water transpired x conc. in nutr. solution

16 Relationship between the lipophilicity of non-ionised chemicals and their translocation to barley shoots via root uptake from nutrient solution Transpiration Stream Concentration Factor TSCF = 0.784exp -[(log Kow ) 2 /2.44] ( ) Log Kow Mean over 24 & 48 h Carbamoyloximes Phenylureas Equation

17 Translocation of non-ionised pesticides from roots to shoots - conclusions Translocation is an equilibrium process, rapidly attained and limited by the Casparian Strip Movement across the membranes is optimal at log Kow 1.8, and less for more polar or more lipophilic compounds Translocation is a passive process (TSCF < 1.0)

18 Conclusions Uptake and translocation into plants from soil water are controlled by the physicochemical properties of the compound But difficult to model due to uncertainties in the distribution of the compound in soil, the distribution of roots and the source of water Vapour transport, important for the more lipophilic compounds both in soil and above soil, is difficult to quantify Metabolism in the plant reduces accumulation