Root Uptake and Xylem Translocation of Pesticides from Different Chemical Classes

A pressure-chamber technique was used to study the root uptake and xylem translocation of some fungicides, herbicides and an insecticide from different chemical classes in detopped soybean roots. Physiological parameters such as K⁺ leakage from roots, K⁺ concentrations in the xylem sap, and protein and ATP levels in the root cells were measured so as to evaluate any potential damage of this technique to the root system. HPLC was used to quantify the compounds in the xylem sap. The pressure-chamber technique has proved useful to study the root uptake and translocation of pesticides, does not damage the root system, and allows one to obtain appreciable volumes of xylem sap that can be analysed directly by HPLC, thus avoiding dependence on the availability of radio-labelled compounds. The concentration of each pesticide in the xylem sap showed a steady-state kinetic profile. Non-linear regression analysis was used to calculate the steady-state concentration and the time required to achieve 50% of the steady-state concentration (TSSC₅₀). TSSC₅₀ was well correlated with log K_ow; the more lipophilic the compound the more time was required to reach the steady-state concentration. The efficiency of translocation was assessed by the transpiration stream concentration factor (TSCF) and a non-linear relationship between TSCF and log K_ow was observed. The highest TSCF values were measured for those compounds with log K_ow values around 3, a lipophilicity value similar to that reported earlier in an analogous experiment with detopped soybean plants but slightly higher than that reported in earlier experiments with intact barley plants. Lower TSCF values were obtained with chemicals with log K_ow values below as well as above 3. © 1997 SCI.     

Physicochemical factors affecting the uptake by roots and translocation to shoots of amine bases in barley

The uptake by barley roots from nutrient solution and subsequent transport to shoots of two series of amine bases were measured over 6 to 72 h. The compounds were chosen to span systematically ranges of lipophilicity (assessed using 1-octanol/water partition coefficients, K_ow) and pKa that would include commercial pesticide amines. In a series of six substituted phenethyl amines, strong bases with pKa∽9·5, all the compounds were strongly taken up by roots from solutions of pH 8·0; uptake declined substantially as the pH was lowered to 5·0, especially for the compounds of intermediate lipophilicity (log K_ow 2 to 3). This uptake could be ascribed to three processes: (i) accumulation of the cation inside the root cells due to the negative charge on the plasmalemma, as given by the Nernst equation and important only for the polar compounds which have low permeation rates through membranes; (ii) accumulation into the vacuole by ion-trapping, which was the dominant process at high pH for all compounds and at all pH values for the compounds of intermediate lipophilicity; (iii) partitioning on to the root solids, substantial only for the most lipophilic compounds. Translocation to shoots was proportional to uptake by roots, this ratio being independent of external pH for each compound and being optimal for the compounds of intermediate lipophilicity. Such proportionality was also observed in a series of three weaker bases of intermediate lipophilicity, in which compounds of pKa 7·4 to 8·0 were also well taken up and translocated whereas the very weak base 4-ethylaniline (pKa 5·03) was much less so. Tests with quaternised pyridines confirmed that organic cations move only slowly through membranes. The observed behaviour of the amines could be modelled reasonably well assuming that transport within the plant was dominated by movement across membranes of the non-ionised species, and this appeared to be true even for the most lipophilic phenethylamine (log K_ow 4·67) studied, though its long-distance movement would be as the protonated species. © 1998 Society of Chemical Industry     

Application of reverse-phase h.p.l.c. for the determination of partition coefficients

Reverse-phase high performance liquid chromatography (h.p.l.c.), using a C₁₈ analytical column, has been applied to the determination of partition coefficients for a range of agrochemicals and industrial chemicals. Using a correlation plot of the logarithm of the capacity factor (k) with the logarithm of the n-octanol/water partition coefficient (P_ow), partition coefficients were predicted with a 95% tolerance interval of ± log 0.80 of the literature ‘shake flask’ value for compounds of random structure over the log P_ow range 0–6. Individual regression lines were fitted for compounds of comparable size and functional grouping, which reduced any bias and thereby enabled more accurate predictions to be made. The reverse-phase h.p.l.c. method has a number of advantages over the traditional ‘shake-flask’ method. Quantitative methods are not required or do not have to be developed and only the determination of the retention time is necessary. Quick and precise determinations of retention times are facilitated by h.p.l.c. and further improvement can be obtained by automation of solvent mixing, solute injection and data processing. H.p.l.c. was used to generate partition coefficient data for highly hydrophobic materials and, because of its resolving power, data for mixtures and solvent fractions. Dual detection, using u.v. and r.i. in series, was necessary for some compounds, particularly unknown mixtures and impure compounds. Calculations of log P_ow based on the fragment-addition method using the structural data file, MACCS, was of considerable value in confirming experimentally derived values. In certain cases, calculated log P_ow values were considered more trustworthy than experimental values.     

Polydisperse ethoxylated fatty alcohol surfactants as accelerators of cuticular penetration. 1. Effects of ethoxy chain length and the size of the penetrants

The effects of polydisperse ethoxylated fatty alcohol (EFA) surfactants on the penetration of six organic compounds varying in size (molar volumes, 107–282 cm³ mol^-1) and lipophilicity (log K_ow 0·8–6·5) were investigated using astomatous isolated cuticular membranes (CM) of Citrus and pear leaves. Mobilities of model compounds in CM were measured by unilateral desorption from the outer surface (UDOS). Rate constants (k*) obtained in these experiments are directly proportional to diffusion coefficients and, in the absence of EFA, k* values decreased by a factor of 52 when molar volumes increased only 2·64-fold. Under UDOS conditions using micellar surfactant solutions as desorption media, surfactants are sorbed in the CM and the volume fractions sorbed were found to decrease from approximately 0·062 to 0·018 when the average number of ethoxy groups (nE) increased from 5 to 17. In the presence of the EFA surfactants in the CM, solute mobilities increased markedly though this effect diminished with increasing nE. Surfactants with nE=17 affected solute mobilities only marginally. Surfactant effects on solute mobility increased with the size of the solutes leading to almost identical mobilities of the model compounds. With the current range of our model compounds, lipophilicity increased with increasing molar volumes, though evidence is presented showing that the mobilities of solutes depend on their molar volumes while lipophilicity has no effect. Effects of micellar aqueous solutions of polydisperse surfactants on solute mobilities followed the pattern observed with monodisperse ones. © 1997 SCI     

Modelling uptake into roots and subsequent translocation of neutral and ionisable organic compounds

A study on uptake of neutral and dissociating organic compounds from soil solution into roots, and their subsequent translocation, was undertaken using model simulations. The model approach combines the processes of lipophilic sorption, electrochemical interactions, ion trap, advection in xylem and dilution by growth. It needs as input data, apart from plant properties, log K_OW, pK_a and the valency number of the compound, and pH and chemical concentration in the soil solution. Equilibrium and dynamic (steady‐state) models were tested against measured data from several authors, including non‐electrolytes as well as weakly acidic and weakly basic compounds. Deviations from the measured values led to further development of the model approach: sorption in the central cylinder may explain the small transpiration stream concentration factor of lipophilic compounds. For non‐electrolytes, the model predicted uptake and translocation with high accuracy. For acids and bases, the tendency of the results was satisfactory. The dynamic model and the equilibrium approach gave similar results for the root concentration factor. The calculation of the transpiration stream concentration factor was more accurate with the dynamic model, but still gave deviations up to factor of ten or more. The dominating process for monovalent weak electrolytes was found to be the ion trap effect. © 2000 Society of Chemical Industry     

Uptake and translocation of bleaching herbicidal compounds in radish seedlings

The relationship between the hydrophobicity of certain herbicidal compounds and the bleaching pattern caused on radish cotyledons was investigated. Seed treatment with diphenylpyridones, as well as with established herbicides, produced three types of bleaching pattern according to their hydrophobicity. The less hydrophobic compounds caused complete bleaching of both cotyledons, but the compounds with more hydrophobicity caused only partial bleaching. The critical points for whole or partial bleaching were in the range of log K_ow 4–5 (K_ow: octanol/water partition coefficient), and these values were changed slightly with their chemical classes. Uptake of compounds into the seed coat took place rapidly; these compounds were then translocated slowly from the seed coat to the embryo, namely, radicle, abaxial surface of one cotyledon and marginal areas of both cotyledons. Application of these compounds to roots resulted in initial translocation to marginal areas of both cotyledons, with subsequent translocation to the middle area. It is believed that compounds taken up into the radicle were translocated to both cotyledons in a manner similar to that following application to roots. These effects following uptake by seeds can be used as a translaminal and lateral transport assay for bleaching herbicidal compounds in cotyledons.     

Recent developments in our understanding of the plant cuticle as a barrier to the foliar uptake of pesticides†

The plant cuticle is a highly complex membrane which forms the outer surface of the aerial portion of plants. The nature of the plant cuticle is reviewed with particular regard to its action as a potential barrier to the penetration of pesticide molecules; the role of the cuticular waxes is highlighted. The physicochemical properties of the cuticle influence the behaviour of spray droplets and, in turn, may affect the rate and efficiency of cuticle penetration. The permeation of active ingredients is influenced by their solubility characteristics as indicated by octanol/water (log K_ow) and cuticle/water (K_cw) partition coefficients. Penetration of hydrophilic compounds (low log K_ow) may be enhanced by hydration of the cuticle, while transcuticular transport of non-polar solutes (high log K_ow) is increased by factors which reduce wax viscosity. The use of in-vitro models involving isolated cuticle membranes, isolated cuticle waxes, or isolated leaves has helped to focus on the activities of the cuticle in the absence of other physiological factors. Using these systems, the role of the waxes as a transport-limiting barrier has been identified and the factors influencing sorption, permeance and desorption examined. The action of surfactants, in vitro and in vivo, has been briefly addressed in regard to their role in facilitating cuticle penetration; other steps involving surfactant/solute/cuticle are complex, and synergy appears to depend on a number of factors including test species, concentration of active ingredient, surfactant type and concentration. Adjuvants may greatly influence the surface properties of the droplet, predispose the cuticle to solute transport, and enhance pesticide activity. The nature of these complex inter-relationships is discussed. © 1999 Society of Chemical Industry     

Kinetics of the reaction of the first metabolite of fenitropan with some low molecular weight thiols

2-Nitro-I-phenylpropen-3-yl acetate (NPPA), the first metabolite of the fungicide fenitropan, reacted readily with glutathione in aqueous ethanol solutions at room temperature, producing at least two products. The first reaction step, which is believed to be a bimolecular nucleophilic (Michael) addition, had a strongly pH-dependent reaction rate. Second-order rate constants were calculated for the reactions of NPPA at pH 4 with glutathione and with some other low molecular weight thiols. Nucleophilic reactivity of the reacting thiolate anions is linearly related to the pK_a values of the thiols. However, as the concentration of thiolate anion is also determined by the thiol pK_a, there is no simple relationship between second-order rate constants and thiol pK_a. Thus the blocking rate of the various essential sulphydryl groups in fungi by NPPA is determined by the sulphydryl pK_a values and the ambient pH value.     

A nonlinear, dynamic, simulation model for transport, and whole plant allocation of systemic xenobiotics following foliar application. IV: Physicochemical properties requirements for optimum absorption and translocation

The relationship between the physicochemical properties (molar volume, partition coefficient, and dissociation constant) of slow-acting systemic postemergence xenobiotics and their uptake and translocation to the sites of action was investigated using the nonlinear, dynamic simulation model ERMESSE. When the pK_a was held constant at 4.0, the model enables the prediction of the uptake of a systemic xenobiotic as a function of its partition coefficient and molar volume. The model also considered the effects of the physicochemical properties of a systemic xenobiotic on its long-distance translocation within the vascular tissues. For instance, when the log K_ow and pK_a were held constant at 1.5 and 6.0, respectively, the model predicted a higher translocation rate (55%) for molecules with a small (e.g., MV = 100 cm³ mol⁻¹) as opposed to a large (e.g., MV = 300 cm³ mol⁻¹, 33%) molar volume. In addition, the theoretical predictions from the ERMESSE model showed that any xenobiotic with a molar volume not exceeding 300 cm³ mol⁻¹ could provide an uptake ?50% and a translocation rate ?25% when its log K_ow is between −0.5 and 2.5 and its pK_a is between 0.0 and 8.0.     

Physico-chemical factors determining the phloem translocation of benzoic acids

A series of ¹⁴C-labelled benzoic acids, chosen to permit assessment of the role of pK_a and lipophilicity in determining movement in plants of these herbicide analogues, was synthesised and their phloem translocation investigated. Following application of substituted benzoic acids to castor bean, Ricinus communis L., by injection into the petioles, the compounds of intermediate lipophilicity (2-fluoro-, 4-chloro- and 3,4-dichlorobenzoic acids) gave highest concentrations in phloem exudates; 4-methyl-2,3,5,6-tetrafluoro- and pentafluorobenzoic acids were less well translocated, perhaps because their pK_a values are much less than those of the other benzoic acids studied. The polar 4-ureidobenzoic acid and the lipophilic 3-(4-methylphenoxy)benzoic acid were much less efficiently translocated in phloem. These results are similar to those previously obtained for phenoxyacetic acids, and provide further support for the role of ionisation in the accumulation and retention of chemicals in phloem sieve tubes.     

Synthesis and fungicidal activity against Pyricularia oryzae of 6-(1,2,4-triazol-4-yl) chromone and -1-thiochromone derivatives

A series of novel 6-(1,2,4-triazol-4-yl) chromone and -1-thiochromone (benzo[b]thiazin-4-one) derivatives was obtained by cyclisation via thiosemicarbazides which were prepared by reaction of hydrazines and the corresponding isothiocyanates. Their fungicidal activity was evaluated against the rice blast fungus Pyricularia oryzae. Of this series, 2,5,8-trimethyl-6-(1-propyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl) chromone, 6-(1-butyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone, 6-(1-hexyl-3-methyl-5-thioxo-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone and 6-(1-allyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone were highly active (pEC₅₀>6·0). Structure–activity relationship studies using the capacity factor k′ as a hydrophobicity index suggested that the log k′ optimum for 2,5,8-trimethyl-chromone and -1-thiochromone derivatives was around 1·0, equivalent to a log P_ow value of c. 4·4. © 1998 SCI     

Sorption of atrazine and dicamba in Delaware coastal plain soils: a comparison of soil thin layer and batch equilibrium results

The mobility and retention of atrazine and dicamba in six Atlantic Coastal Plain soils were estimated by soil thin-layer chromatography (soil-TLC). The soils studied were representative of the major agricultural regions in Delaware and were sampled, by horizon, to the water table. Four horizons from each profile were leached simultaneously with distilled water on one soil-TLC plate. Two values were obtained from each plate: the ratio of the distance traveled by the herbicide center of mass over that traveled by the solvent front (R_m), and a sorption distribution coefficient (K_d). The R_m values ranged from 0·06 to 0·94 for atrazine and from 0·80 to 0·94 for dicamba. Herbicide mobility was found to be greatest in coarse-textured soil horizons that contained low levels of organic matter, clay, and Fe and Al oxides. Correlation analysis indicated that effective cation exchange capacity, exchangeable acidity, exchangeable aluminum, and clay were useful predictive variables or both atrazine mobility and sorption. Organic matter was not useful for predicting soil-TLC derived sorption estimates; however, it was correlated to K_d-batch estimates. Distribution coefficients calculated from soil-TLC data were found to be in general agreement with K_d values obtained for the same soils by batch equilibrium techniques. The average K_d-soil-TLC values for atrazine and dicamba were 2·09(±2·24) and 0·03(±0·02), respectively. The ratio of the batch K_d to the soil-TLC K_d ranged from 0·1 to 19 (x̄=1·6, SD=3·8) for atrazine and from 2·9 to 38 (x̄=12·6, SD=8·7) for dicamba. Thus, although for some horizons agreement between the two methods was good, for other horizons significant discrepancies existed. It is suggested that the soil-TLC gives results under non-equilibrium conditions, whereas the batch procedure is, by definition, at quasi-equilibrium. These fundamental differences may account for the observed differences between the two methods. It is also suggested that, due to this difference, the soil-TLC procedure can provide additional information relevant to herbicide partitioning in the field environment that is not provided by traditional batch equilibrium techniques. © 1998 Society of Chemical Industry     

五种加工方式对黄瓜中10种农药残留的去除效果

在实验室模拟沉积农药条件下,通过液相色谱-串联质谱 (LC-MS/MS) 和气相色谱-串联质谱 (GC-MS/MS) 检测技术,研究了经水洗、水煮、炒制、去皮和腌制5种加工方式后,多菌灵、吡虫啉、啶虫脒、乙霉威、霜霉威、丙溴磷、氯氰菊酯、三唑磷、敌敌畏和嘧霉胺10种农药在黄瓜中的残留量变化情况。结果表明:在5种加工方式中,以去皮处理对农药的去除效果最明显,其中丙溴磷和氯氰菊酯的加工因子 (PF) 均为0.04,其他4种加工方式对农药去除效果的强弱顺序为水煮>炒制、水洗、腌制;农药的log K_ow(辛醇水分配系数) 值跟农药的去除效果直接相关,经水洗和水煮2种加工方式处理后,农药的log K_ow值越小,越易被去除。另外,水洗、水煮和炒制处理,在0~10 min内随处理时间延长农药残留量呈减小的趋势,10种农药的PF变化范围为:水洗时PF在1.00~0.62之间,水煮时PF在0.86~0.37之间,炒制时PF在1.13~0.52之间。     

Screening Test for Insecticides Interfering with Cuticular Sclerotization

The potential of known and new insecticides to interfere with cuticle sclerotization was investigated using assays for key enzymes such as phenoloxidase, quinone methide isomerase and DOPA decarboxylase. Homogenates from the blowfly Lucilia cuprina and from the epithelial cell line from Chironomus tentans were used to examine the compounds under investigation. Phenoloxidases are known to oxidize DOPA, the substrate for DOPA decarboxylase. Since phenoloxidases were not detectable in C. tentans cell homogenates, inhibitor and kinetic studies were done for comparison with DOPA decarboxylase of this insect cell line. DOPA decarboxylase and phenoloxidase of L. cuprina exerted highest specific activities at early pupal stages (day 7). The apparent K_m values for the two enzymes were 0·47(±0·21) mM and 0·71(±0·16) mM , respectively, using L -DOPA as substrate. DOPA decarboxylase from C. tentans had a K_m value of 0·42(±0·18) mM . Quinone methide isomerase was most active in young pupae. In terms of substrate specificity for enzymic (mushroom-tyrosinase) production of different quinones from their corresponding catechols, that with dopamine quinone proved to be the most efficient. Synthesis of derivatives of L -DOPA and L -tyrosine led to a compound which inhibited both phenoloxidase and quinone methide isomerase. DOPA decarboxylase from L. cuprina and from cells of C. tentans was inhibited by carbidopa (IC₅₀ values of 0·021(±0·011) μM and 0·031(±0·019) μM , respectively) and indomethacine (IC₅₀ values of 22·6(±7·1) μM and 18·8(±9·7) μM ). Both compounds exerted a competitive type of inhibition and were able to interfere with development of L. cuprina.     

Synthesis and Structure–Activity Relationships of Miticidal 4,5-Dihydropyrazole-5-thiones

A series of novel 4,5-dihydropyrazole-5-thiones (DHPs) was synthesised by treating the corresponding dihydropyrazolones with ‘Lawesson’s reagent and evaluated for miticidal activity against two-spotted spider mites (Tetranychus urticae Koch). Of these, 3-(4-chlorophenyl)-4,4-dimethyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-4-ethyl-4-methyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-1-phenyl-4,5-dihydropyrazole-5-thione-4-spirocyclopentane and 4,4-dimethyl-1-phenyl-3-(4-trifluoromethyl-phenyl)-4,5-dihydropyrazole-5-thione were highly active (pEC₅₀>4·0) and were more effective than the miticide dicofol (pEC₅₀=3·879), which has traditionally been used for the control of phytophagous mites. Structure–activity relationship (SAR) studies were performed on each position of the pyrazole ring of DHPs. The results indicated that the unsubstituted phenyl, 4-substituted phenyl and thioxo groups on the 1-, 3- and 5-positions of DHPs respectively were required for activity. Quantitative SAR studies using physicochemical parameters of substituents and the capacity factor k′ as a hydrophobicity index suggested that: (a) the activities of all types of DHPs examined were mainly dominated by hydrophobicity, (b) the bulkiness of 4-substituents of the 3-phenyl ring favoured the activity and (c) the log k′ optimum for all DHPs was 1·675, equivalent to a log P_ow value of c. 5·0.     

Relationships between lipophilicity and the distribution of non-ionised chemicals in barley shoots following uptake by the roots

Determinations were made of the distribution of two series of non-ionised chemicals, ^O-methylcarbamoyloximes and substituted phenylureas, in barley shoots, following uptake by the roots from solution. The concentrations in basal and central shoot sections became constant after 24 to 48 h for all but the most lipophilic chemical studied, and were then greatest for the more lipophilic chemicals. Amounts in the leaves generally increased up to 72 or 96 h, when degradation balanced translocation. The accumulation of chemical in the lower section of shoots can be ascribed to a partitioning process similar to that in roots, the chemical being partitioned between the shoot and the xylem transpiration stream; this uptake could be estimated from the octan-1-01/water distribution coefficients, and was predicted to be greatest for compounds for which log K_ow=4. 5.     

Relative solubilities of bifenox and 1-naphthylacetic acid (NAA) in plant cuticles and in selected pure or aqueous glycol additives

The driving force for foliar penetration is the product of the partition coefficient (K) between the cuticle and the formulation residue, and the concentration of the active ingredient in the spray residue. Ethylene glycols and polyethylene glycols (PEGs) are often contained in commercial formulations, because they are good solvents and not toxic. Since they are humectants, the water content of the formulation residue varies with humidity of the air. At 25°C and 65% relative humidity PEG 400 contains about 50% water. The partition coefficients for the lipophilic herbicide, bifenox, increased with increasing water content of the ethylene glycols and PEGs, such that log K was a linear function of the mass fraction of water or PEG. The K value was about 0·5 for the system cuticle/pure PEG and 27500 for the system cuticle/water. When PEG contained 50% water, K was only 110. Partition coefficients of bifenox between cuticle and ‘Tween’ 80 depended also on humidity, having values of 0·75 in cuticle/pure ‘Tween’ 80 and 29·1 when ‘Tween’ 80 contained 50% water. With 1-naphthylacetic acid (NAA), which is a weak acid, partition coefficients also depended on water content of PEG 400, but a maximum curve was obtained. The maximum partition coefficient (211) was observed with a mixture of 30% PEG 400 and 70% water, which corresponded to a humidity of 88%. We suggest that this is due to an effect of PEG 400 on the ionisation of NAA. Our data demonstrate that partition coefficients are affected by humidity, because solubilities of lipophilic compounds and weak acids in PEG/water mixtures vary greatly with the water content. This in turn affects driving forces, mainly by the effect of humidity on partition coefficient. With non-ionisable lipophilic compounds, partition coefficients, driving forces and rates of foliar uptake therefore increase with increasing humidity. © 1998 SCI     

Comparative SAR Evaluations of Annonaceous Acetogenins for Pesticidal Activity

The activities of 44 Annonaceous acetogenins, which were originally isolated by monitoring plant fractionations with the brine shrimp lethality test (BST), were evaluated in the yellow fever mosquito larvae microtiter plate (YFM) assay. The results clearly demonstrate that most acetogenins have pesticidal properties. The structure–activity relationships indicate that the compounds bearing adjacent bis-THF (tetrahydrofuran) rings with three hydroxyl groups are the most potent. Bullatacin ( 1 ) and trilobin ( 7 ) gave the best activities against YFM with LC₅₀ values of 0·10 and 0·67 mg litre^-1, respectively. Compounds showing LC₅₀ values below 1·0 mg litre^-1 in this assay are usually considered significant as new lead candidates for pesticidal development. In the BST, the corresponding LC₅₀ values were 1·6×10^-3 ( 1 ) and 9·7×10^-3 ( 7 ) mg litre^-1. This is the first report of pesticidal structure–activity relationships for a series of Annonaceous acetogenins which are known to act, at least in part, as potent inhibitors of mitochondrial NADH: ubiquinone oxidoreductase. © of SCI.     

Transport via xylem of atrazine, 2,4-dinitrotoluene, and 1,2,3-trichlorobenzene in tomato and wheat seedlings

Transport of atrazine (ATR), 2,4-dinitrotoluene (DNT), and 1,2,3-trichlorobenzene (TCB) from roots to shoots via xylem of wheat and tomato seedlings was measured following a 24-h exposure of plant roots to hydroponic solutions of these organic compounds. Transport of the compounds from roots to shoots reached equilibrium within 24 h, consistent with an earlier finding. Low concentrations of TCB were detected in the final external solution and the xylem efflux of control wheat seedlings. This suggested that there was a fast foliar uptake of TCB and its downward movement via phloem of the wheat seedlings. Concentrations of DNT, ATR, and TCB in xylem effluxes of wheat and tomato increased significantly with increases of their external concentrations. The translocation stream concentration factors (TSCF), i.e., the ratios of the concentrations in xylem sap to those in external solution, of the compounds with tomato seedlings followed the order of ATR > DNT >> TCB, which was inversely correlated with the log K_ow (the octanol–water partition coefficient) of the compounds. The observed xylem transports of DNT and TCB from roots to shoots with wheat seedlings were lower than those with tomato seedlings. ATR exhibited a high xylem transport with the two plant species, which resulted presumably from an atrazine–metal complex formation.     

Transformation of 3-Chloroallyl Alcohol in Water-Saturated Subsoil Studied with a Column Method

The performance of a newly developed column method for pesticide transformation rate measurements in the subsoil was tested using (Z)- and (E)-3-chloroallyl alcohol as model compounds. Sandy anaerobic water-saturated subsoil was collected at between 1·8 and 2·3 m below the surface of a flower-bulb field. Transformation rates were measured using subsoil columns that were filled in situ and were compared with the transformation rates in laboratory incubation systems. In the column experiment the half-life ranged from 0·5 to 5·2 days for (Z)-3-chloroallyl alcohol and from 1·0 to 5·5 days for (E)-3-chloroallyl alcohol. The capacity of the saturated subsoil for transformation of both isomers increased in the course of the column experiment. In the incubation experiment the 3-chloroallyl alcohols were transformed gradually in the first three days, with a half-life of 1·9 days for both isomers. Thereafter the transformation rate accelerated. The general conclusion is that the column method yields results similar to those of the incubation method for these rapidly transforming compounds.