Colloids and Surfaces A: Physicochem. Eng.

Aspects 306 (2007) 4955

Interaction of pesticides with a surfactant-modied soil interface: Effect of soil properties

M.C. Hern ndez-Soriano, M.D. Mingorance, A. Pe a a n
Departamento de Ciencias de la Tierra y Qumica Ambiental, Estaci n Experimental del Zaidn (CSIC), c/Profesor Albareda, 1, E-18008 Granada, Spain o Received 6 July 2006; received in revised form 14 November 2006; accepted 15 November 2006 Available online 22 November 2006

Abstract Adsorption of four organophosphorous insecticides, diazinon, dimethoate, malathion and methidathion, on nine soils representative of the Mediterranean area was studied. The sorption of the organophosphorous pesticides was slightly inuenced by soil texture and organic matter content. Pesticide sorption was ranked according to their hydrophobicity, except for the pair diazinon/malathion. Pesticide sorption was also examined in aqueous solutions in the presence of surfactants. Three different surfactants were selected: a cationic (hexadecyl trimethyl ammonium bromide), a non-ionic (Tween 80) and an anionic surfactant (Aerosol 22), to verify the effect of their presence on pesticide retention by the different soils. The addition of Tween 80 and Aerosol did not modify the pesticide sorption and no correlation was found between soil organic matter and clay content and pesticides sorption coefcients. The presence of the cationic surfactant increased pesticide retention, especially when the surfactant was present at a concentration between 100 and 200% of the soil cation exchange capacity. In the presence of the cationic surfactant, the distribution coefcients were signicantly correlated with soil exchange capacity. The competition between the weakly retained dimethoate and the other insecticides was tested in the presence or absence of the cationic surfactant. Dimethoate has showed a higher retention when examined alone than when the rest of the insecticides competed for sorption sites. 2006 Elsevier B.V. All rights reserved.
Keywords: Organophosphorous pesticides; Sorption; Soil; Surfactants; Competition

1. Introduction Pesticides enter the environment due to their application with agronomic purposes. Once in the soil the pesticides can be absorbed by the plants to control the target pests or remain in the substrate until degraded by different biotic and abiotic processes or transported to other environmental compartments, such as deeper soil layers or groundwater. Pesticides, like other organic pollutants, are retained by the soil according to their physicochemical properties and to the soil nature and composition. Sorption potential is mainly controlled by organic carbon (OC) and soil clay content [13]. To evaluate sorption potential it is necessary to take into account OC and clay data together with other soil properties, such as texture and composition. However, other compounds present in this environmental medium may affect the relationship between pesticide and soil. According to Abu-Zreig et al. [4], surfactants are the most abundant organic compounds in wastewaters from

domestic use. For instance, surfactant use in the USA was estimated in 2.2Mg [5] and their presence in treated wastewaters may range from some hundreds of mg L1 to several g L1 [6]. Surfactants of different nature have been found in soils treated with sludges or irrigated with wastewaters [79] and their presence may affect the retention and mobility of metals and organic compounds, such as pesticides [1013]. Surfactants in aqueous solution tend to accumulate in the liquid/gas or solid/liquid interfaces leading to an increment in the distance of water molecules hence reducing the water surface tension [4]. The aim of the present work is to evaluate the effect of soil properties on the sorption of organophosphorous insecticides on various soils representative of the Mediterranean area as affected by the presence of surfactants of different nature. 2. Material and methods 2.1. Materials Nine soils samples were collected from the top (025 cm) soil layer from various locations in Granada (Spain). Soil

Corresponding author. Tel.: +34 958 181600; fax: +34 958 129600. E-mail address: arancha@eez.csic.es (A. Pe a). n

0927-7757/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2006.11.030

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M.C. Hern ndez-Soriano et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 306 (2007) 4955 a

samples were air dried, crushed and sieved through 2 mm mesh. The particle size distribution was determined by sieving and sedimentation, applying the Robinsons pipette method [14] after organic matter had been removed with H2 O2 , using sodium hexametaphosphate as dispersing agent. Organic carbon content was determined by a modied Walkey and Black method [15]. Total calcium carbonate was determined by the pressure gauge method after reaction with HCl [16]. Soil pH values were measured in slurries made up at a 1:2.5 soil/water ratio. Cation exchange capacity (CEC) was analysed by a method based on the triethylenetetramineCu complex [17]. The relative standard deviation of four replicated samples ranged between 5% for measurements depending on chemical determinations, such as pH, OC or CEC, and 15% for granulometric measurements. To verify the inuence of soil organic matter (OM) on pesticide sorption the OC content of soil 9 was partially removed by treatment with H2 O2 , resulting in a nal 0.44% OC content. Commercial humic acid (Fluka, Madrid, Spain) and bentonite from Cabo de Gata (Almera, Southeastern Spain) were also used, because humic acids represent one of the main components of soil organic matter and smectite, which constitutes a 90% of the bentonite, represents a constituent of the clay fraction. The bentonite consists of quartz, plagioclase, potassic feldspar, calcite and trydimite as accessory minerals. Its CEC is higher than 100 meqz /100 g and 42% Ca, 33% Mg, 23% Na and 2% K are present in the exchange complex. Total specic area is 659 m2 g1 .

are 0.0185, 0.354 and 0.653 g L1 , respectively. The latter two were prepared at twice the cmc and HDTMA was prepared at two concentration levels, 1 and 100% of the cation exchange capacity of soil 5, which had the highest CEC of all the studied soils (Table 1). 2.3. Pesticide sorption Pesticide sorption was obtained using a batch equilibration method, with 2.5 g soil, 1 g bentonite or 0.125 g a humic acid. The samples were mechanically shaken end-over-end in a thermostatic chamber at 15 1 C for 24 h, with 10 mL of a solution containing a mixture of the four insecticides at 20 mg L1 . The solutions were prepared from a pesticide solution in acetone at 1 g L1 , by dilution in water or in an aqueous solution containing the different surfactants at the concentrations indicated above. The content in acetone was about 2% in volume, so that it could not have an effect on adsorption [19,20]. Then the samples were centrifuged at 3000 rpm and 15 C for 15 min. An aliquot was sampled for the insecticide analysis. The sorption process was carried out in duplicate with a control of the insecticides solution without soil, to account for possible degradation during the adsorption process. Independent sorption studies containing only dimethoate solutions were run with natural soil and soil modied with HDTMA at 100% of the CEC of soil 5, to check if competition between dimethoate and the other insecticides was taking place. The difference between initial and equilibrium pesticide concentrations was attributed to sorption by soil. The sorption equilibrium distribution coefcient Kd (L kg1 ) was calculated as Kd = X/Ce , where X is the concentration of the pesticides in soil (mg kg1 ) and Ce is the pesticide concentration (mg L1 ) at the equilibrium solution. 2.4. Extraction and analysis In a closed PTFE tube, 5 mL of the supernatant was vortexed with 10 mL ethyl acetate. The mixture was extracted in a microwave oven (Mars Xpress, CEM, Matthews, NC) ramping for 10 min to 90 C, and then maintained for 2 min. The mixture was frozen in a conventional freezer (18 C) and the organic

2.2. Chemicals Four organophosphorous insecticides, with a wide range of physicochemical properties, were selected: diazinon, dimethoate, malathion and methidathion, all with purity 97.5% (Dr. Ehrenstrofer, Augsburg, Germany). Their octanol/water partition coefcients (log Kow ) are 3.3, 0.70, 2.75 and 2.2 and their water solubilities 60, 23300, 145 and 200 mg L1 , respectively [18]. Three surfactants were considered, the cationic hexadecyl trimethyl ammonium bromide (HDTMA), the non-ionic Tween 80 (TW80) (both from Aldrich, Madrid, Spain) and the anionic Aerosol 22 (A22) (Sigma, Madrid, Spain). The critical micellar concentrations (cmc) of HDTMA, Tween 80 and Aerosol 22
Table 1 Characteristics of the soils employed Soil S1 S2 S3 S4 S5 S6 S7 S8 S9 pH 7.9 8.1 7.9 7.8 7.9 7.9 6.8 7.9 8.5 OC (%) 0.62 0.82 1.10 1.08 1.44 1.17 3.51 2.43 0.92 Sand (%) 9.93 19.37 26.01 31.02 7.34 23.02 66.74 36.10 31.00 Silt (%) 39.20 49.69 41.32 29.62 49.12 49.84 25.50 42.37 58.00

Clay (%) 50.87 30.95 32.67 39.36 43.54 27.14 7.76 21.53 11.00

Texture USDA Clay Slity clay loam Clay loam Clay loam Silty clay Clay loam Sandy loam Loam Silty loam

CEC (meqz /100 g) 18.3 12.3 9.8 18.7 24.6 18.0 5.7 9.3 7.9

Carbonate 42.10 58.66 62.12 45.96 28.12 3.09 0.60 13.99 24.90

CEC, cation exchange capacity; OC, organic carbon.

M.C. Hern ndez-Soriano et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 306 (2007) 4955 a

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Table 2 Distribution coefcients (Kd ) for diazinon, dimethoate, malathion and methidathion on different soils, in the presence or absence of different surfactants

2.5. Statistical analysis Correlations among variables and distribution coefcients were carried out by the Pearsons correlation coefcient; comparisons among means by non-parametric tests (SPSS 12.01, Illinois, USA). 3. Results and discussion The main soil characteristics determined are shown in Table 1. The soils have different textures, whilst their pH range is narrow (6.88.5). They present a dominance of high carbonate content as corresponds to calcareous soils. The CEC ranges from low to medium values and they all have lowmedium OC content. According to their granulometry, the soils have been grouped in three textural classes: clayey (T1: soils 1 and 5), clay loamy (T2: soils 2, 3, 4 and 6), and loamy soils (T3: soils 7, 8 and 9). Distribution coefcients (Kd ) are shown in Table 2 for all the experiments. They will be discussed independently according to the nature of the pesticide solution employed. 3.1. Pesticide sorption by soils in aqueous solution The distribution coefcients (Kd ) were ranked, except for malathion, according to the compounds Kow and water solubility values, i.e., malathion > diazinon > methidathion dimethoate (Table 2; Fig. 1). Dimethoate, which is highly soluble in water, had the lowest retention coefcients, and was poorly retained by any of the soils. With respect to diazinon and malathion, the latter was more tightly sorbed on the different soils, as depicted in Fig. 1. There was no signicant correlation between the Kd values and OC content for the sorption of the different organophsophorous pesticides, when all the soils were considered. However, other reports [21] have revealed scarcely signicant or no correlations between both parameters for soil OM contents below 2%. Since the soils employed have in general low OC content, as it is usual in the Mediterranean area, sorption

S1 S2 S3 S4 S5 S6 S7 S8 S9 S9OMc HAd Bente

Soils

Pesticide solution: W, prepared in water; TW80, in Tween 80 (2 cmc); A22, in Aerosol 22 (2 cmc); HD1, in HDTMA at 1% CEC of S5; HD100, in HDTMA at 100% CEC of S5. Negative values set to zero. S9 without OM. Humic acid. Bentonite. Concentration in the supernatant below the LOD.

HD1 TW80 A22 Malathion

phase transferred to a vial for analysis. Recoveries (n = 6) were 93.3, 80.6, 88.9 and 90.4% for diazinon, dimethoate, malathion and methidathion, respectively. Analysis was carried out by capillary gas chromatography in a 5890 Series II gas chromatograph equipped with a ame photometric detector (FPD) and an automatic injector (6890 Series Injector) (all from Hewlett-Packard). Helium was used as the carrier gas and injector and detector temperatures were 250 and 280 C, respectively. A 1 L sample was injected splitless into a DB-1701 (14%-cyanopropylphenyl methylpolysiloxane) (30 m, 0.25 mm i.d. and 0.25 m lm thickness). Oven temperature was programmed starting at 45 C (1.5 min) and heating at 30 C min1 to 270 C (5 min). Retention times were 10.4, 11.2, 11.8 and 13.5 min, for diazinon, dimethoate, malathion and methidathion, respectively. The relative standard deviations for six replicated measurements ranged between 3.6% for diazinon and 6.5% for dimethoate and methidathion.

HD100 HD1 A22 TW80 HD100 W Methidathion

6.3 7.5 10.9 26.8 31.7 9.9 8.9 7.2 6.4 3.5 322.1 0.1 2.1 1.4 1.4 1.3 2.6
b b

9.9 7.7 11.1 22.4 28.7 12.6 12.6 9.7 9.5

5.5 6.3 9.2 20.7 19.1 8.5 6.8 6.8 6.2

5.1 2.9 26.8 43.1 30.4 15.8 13.7 22.4 2.8

562.1 434.4 431.0 568.6 567.1 379.4 67.8 217.0 176.8

HD100

HD1

A22

0.0 0.0 0.1

0.1

TW80

Dimethoate

0.1 0.1 0.2 0.3

0.4 0.1 28.7

0.2

1.7 1.4 1.4 1.7 1.6 1.4 1.7 1.5 2.3

0.0 0.1

37.9 21.7 19.2 32.1 39.6 19.3 5.2 8.9 8.7

HD100

HD1

TW80

Diazinon

8.7 1.4 3.3 8.4 4.2 3.4 16.3 4.1 3.2 2.8 1166.2 2.0

Wa

16.4 3.4 7.0 15.3 7.4 6.5 25.9 8.3 7.0

10.1 2.5 4.9 9.1 5.2 4.6 12.5 5.9 4.1

A22

9.4 1.2 6.9 37.2 6.9 7.4 19.2 15.2 1.5

750.0 616.1 486.5 720.8 898.6 588.4 73.4 285.4 152.3

3.6 0.9 1.3 3.1 2.2 1.6 7.7 2.2 2.9 1.9 349.6 67.9

5.6 2.5 3.6 5.8 4.2 3.4 10.5 4.8 5.1

2.7 0.5 1.6 2.4 1.7 1.1 4.7 2.2 1.6

1.3 1.9 3.0 8.6 5.6 6.8 13.4 11.2 1.7

469.0 413.1 456.4 486.5 491.6 370.0 112.7 270.7 257.5

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M.C. Hern ndez-Soriano et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 306 (2007) 4955 a

Fig. 1. Box plot comparison of Kd for pesticides, ranked according to increasing Kow values, in soil treated with aqueous solution. The horizontal line inside the box marks the median; the whiskers extending from the upper and lower edge of the box (hinges) indicate the range of the all data; data outliers are marked by empty circles (>1.5 hinge spread) and extreme outliers by asterisks (>3 hinge spread).

results were arranged in three groups according to their OC content: very low (<1%), low (12%) and medium (>2%). As it can be seen (Fig. 2B) mean Kd values for methidathion and dimethoate remained unchanged with respect to the soil OC range. For diazinon a small increase has been observed for soils with OC > 2%, whilst malathion was the most affected by

this parameter, showing an increase when OC values exceeded 1%. Previous reports on phenylureas [22] suggest that the sorption process for organic compounds with polar groups in their molecules, such as organophosphorous insecticides, is more complex than hydrophobic theory suggests, pointing to the existence of specic interactions with the OM and, when the OM content is low, with the soil mineral fraction. The partial removal of OC content from soil 9 resulted in a decreased sorption capacity, especially for malathion, suggesting that soil organic content affected more the hydrophobic than the hydrophilic substances. On the other hand, when a commercial humic acid was tested, the sorption values (Kd in Table 2) followed the Kow patterns, i.e., diazinon > methidathion malathion dimethoate, in accordance with pesticide hydrophobicity. It has also been reported that for soils with low OC content interactions of pesticides with soil inorganic matrix may become more important. Pesticide sorption was not affected by soil texture, excepting malathion, whose retention was enhanced for clayey soils (T1 in Fig. 2A). The role of clay in the different retention observed for pesticides was tested with a bentonite, consisting mainly of smectite. The distribution coefcients obtained indicated (Table 2) that in this clay diazinon retention was low, even lower than in most of the soils. Methidathion distribution coefcient was greatly enhanced, but the highest increase corresponded both to malathion and dimethoate. Both pesticides were not detected in the solution, because their retention on the clay reached nearly 100%. The interaction of malathion with bentonite, much higher than that of diazinon, may be another mechanism contributing to the higher Kd values obtained with this pesticide.

Fig. 2. Mean pesticide Kd values for soils with aqueous solutions (water), or solutions with Aerosol 22 at 2 cmc (A22), Tween 80 at 2 cmc (TW80) and HDTMA at 1% CEC of soil 5 (HD1). (A) Soil textural classes (T1, clayey; T2, clayey loam; T3, loam). (B) Soil OC content.

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However, as described by Hamaker and Thomson [3], soil is a dirty mixture in which many substances compete for places to adsorb. They suggest that OM can be considered as adsorbing on the clay and possibly interfering with other substances. Therefore, the sorption of complex molecules on soil cannot be considered as the sum of the sorption on individual soil fractions. Consequently, the use of a commercial humic acid and bentonite to understand the sorption processes involved is only a slight approximation of the real mechanism. 3.2. Pesticide sorption by soils in TW80 and A22 solutions The concentration used for TW80 and A22 was 2 cmc because, according to previous results [23], this concentration of non-ionic and anionic surfactants had induced the highest retention for organic pollutants in soils. For both surfactants, the distribution coefcients followed in general the same trends observed for aqueous pesticide solutions (Table 2; Fig. 2), without signicant correlation between Kd values and soil OC or clay content. In the case of soil texture, a weak increase was observed for malathion sorption with soil clay content (Fig. 2A). With respect to the soils OC content, as it occurred with aqueous pesticide solutions, malathion and diazinon sorption parameters increased for OC > 1 and 2%, respectively (Fig. 2B). Non-ionic surfactants, such as TW80, can be partially sorbed on soil surfaces inducing a hydrophobic medium where the hydrophobic pollutants can be retained. The sorption of these surfactants is mainly dependent on the soil mineralogy [24,25]. On the other hand, it has been reported for other anionic surfactants that their retention on soil is much lower than that of non-ionic surfactants [24] and that negatively charged compounds are not retained on the soil surface because of repulsions between the similarly charged OM and clay of the soil [26]. In some cases, the observed reduction of sorption was attributed to a solubilization of the pesticides by the surfactant monomers or micelles present in solution, which would desorb the originally retained pesticides. A previous report [27] on the enhancement of diazinon leaching in soil columns in the presence of the anionic surfactant sodium dodecyl sulphate at a concentration above the cmc, supports the results. 3.3. Pesticide sorption by soils in HDTMA solutions HDTMA, a cationic surfactant, was tested at two concentration levels: a low level (HD1) corresponding to 1% of soil 5 CEC with the highest CEC value, and a high level (HD100) accounting for 100% of the same soil CEC. For the low level, which corresponds to ca. 1.5 cmc, pesticide Kd values were similar or slightly higher than those for aqueous pesticide solutions (Table 2; Fig. 2). Signicant differences were found for all the pesticides, except diazinon, among OC content classes (P < 0.05). Soils 1, 2 and 9 with OC content below 1% showed the lowest Kd values (Fig. 2B). Since at this low surfactant level, only a small part of the exchange sites of the soil surface is covered, the soil properties still play an important role in pesticide retention and again Kd values were ranked according

Fig. 3. Logarithms of pesticide Kd values for HDTMA solutions at 100% CEC of soil 5 vs. soil CEC.

to the compounds hydrophobicity (log Kow ), except for the pair diazinon/malathion, as it occurred with soil without surfactant. When HDTMA concentration was increased to the highest value, the distribution coefcients were highly promoted (Table 2). Cationic surfactants may be retained by a cation exchange mechanism displacing the inorganic cations [28]. At the low surfactant level the surfactant monomers are held on the surface in the form of hemimicelles. When the concentration is increased the exchange sites became fully occupied [29] leading to a surface coverage equal to or higher than the monolayer, depending on the soil CEC. This behaviour has been also described for other organic compounds, such as benzene, toluene or ethylbenzene [30]. Kd values for each pesticide showed a signicant correlation (P < 0.05) with soil CEC values (rdiazinon = 0.915, rmalathion = 0.849, rmethidathion = 0.776, rdimethoate = 0.907) (Fig. 3). Therefore, for soils with medium or high CEC values (soils 1, 2, 4, 5 and 6) the surfactant coverage was at its maximum (100200% CEC), forming a monolayer or a weakly retained bilayer, which corresponds to a maximum increase in pesticide retention (Fig. 3). For these soils, Kd values were also signicantly correlated (r = 0.952; P < 0.05) with the pesticides Kow values, since the hydrophobic nature of the surfactant favours a partition of the pesticides into the modied soil. Soils with CEC below 10 meqz /100 g were not able to retain such a great HDTMA quantity and the excess of not bound cationic surfactant formed micelles in solution able to desorb the retained pesticides. This was the case for soils 3, 7, 8 and 9 for which the retention on the modied soil was the lowest. 3.4. Sorption with dimethoate solutions Competition for sorption sites has been one of the mechanisms proposed when several compounds are to be retained by

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M.C. Hern ndez-Soriano et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 306 (2007) 4955 a

calculated for individual compounds, may be altered when other pollutants are also present. 4. Conclusions Among the soils studied ne textured soils have higher sorption capacity and hence show less sensitivity to pesticide leaching. Medium and coarse textured soils show less pesticide retention capacity. The OC content of the soils, which is low for all of them as corresponds to Mediterranean soils, was poorly correlated with pesticide retention and affected more the hydrophobic pesticides, malathion and diazinon. The presence of non-ionic and anionic surfactants in the pesticide solution did not modify pesticide sorption by the soils, which was not correlated with soil properties. However, the presence of the cationic surfactant HDTMA increased pesticide retention, being this increase dependent of surfactant concentration and soil CEC. The pesticide Kd values did not completely follow the compounds hydrophobicities, in particular the pair diazinon/malathion. Malathion, less hydrophobic than diazinon was however more tightly retained by the different soils, which pointed to an interaction with OM and clay soil fractions, possibly due to the presence of polar groups in its molecule. Therefore, general conclusions should be avoided since each system soilpesticide may behave in a non-predicted way, requiring a previous evaluation. Additional studies would be also necessary when various pesticides are present at the same time, since competition effects may be quite signicant, depending on the soils and on the other compounds present in the soil solution. Acknowledgements E. Caballero and C. Jim nez de Cisneros are acknowledged e for the X-ray diffraction measurements. This work was nanced through a regional project from Junta de Andaluca (Ref. C03 044). References
[1] M.C. Fernandes, L. Cox, M.C. Hermosn, J. Cornejo, Pest Manage. Sci. 59 (2003) 545. [2] R.D. Wauchope, S. Yeh, J.B.H.J. Linders, R. Kloskowski, K. Tanaka, B. Rubin, A. Katayama, W. K rdel, Z. Gerstl, M. Lane, J.B. Unsworth, Pest o Manage. Sci. 58 (2002) 419. [3] J.W. Hamaker, J.M. Thompson, in: C.A. Goring (Ed.), Organic Chemicals in the Environment, Marcel Dekker, 1972, pp. 49143 (Chapter 2). [4] M. Abu-Zreig, R.P. Rudra, W.T. Dickinson, Biosyst. Eng. 84 (2003) 363. [5] B.F. Greek Jr., Chem. Eng. News 69 (1991) 25. [6] N. Narkis, B. Ben-David, Water Res. 19 (1985) 815. [7] M. Castillo, E. Martnez, A. Ginebreda, L. Tirapu, D. Barcel , Analyst 125 o (2000) 1733. [8] J. Vikelse, V. Thomsen, L. Carlsen, Sci. Total Environ. 296 (2002) 105. [9] L. Carlsen, M.-B. Metzon, J. Kjelsmark, Sci. Total Environ. 290 (2002) 225. [10] M. S nchez-Camazano, S. Rodrguez-Cruz, M.J. S nchez-Martn, Environ. a a Sci. Technol. 37 (2003) 2758. [11] W.O. Werkheiser, S.J. Anderson, J. Environ. Qual. 25 (1996) 809.

Fig. 4. Changes in Kd (Kd alone /Kd mixture ) values of dimethoate on the different soils in aqueous or in HDTMA solution at 100% CEC of soil 5 (HD100).

the same substrate. Since dimethoate was the less retained insecticide due to its less hydrophobic nature, a set of isotherms was run in the absence of the other insecticides. As it can be seen (Fig. 4) the relative distribution coefcients for dimethoate in all soils was higher when it was the only compound than when it was mixed with the rest of insecticides. The more weakly sorbed dimethoate was less retained when it had to compete with other organophosphorous insecticides for sorption sites. Previous reports of competition have been documented, such as between atrazine and other triazine herbicides or metolachlor [31,32], phorate and terbufos [33], as well as for bromacil, napropamide and prometryn in natural soils [34]. In addition, the competitive effect was also studied for the soils with cationic surfactant solution, which had induced the highest enhancement of pesticide sorption (Fig. 4). As it occurred with natural soils, dimethoate was more tightly sorbed on soil in the presence of the cationic surfactant HDTMA. The competition among compounds for chemicals in soils with surfactants has also been reported [3537]. However, the relative increase was lower and similar for all soils, probably due to the fact that more sites were available for sorption, even when all the pesticides were present, and that the soil surface was covered with the surfactant offering similar interaction sites to the organophosphorous insecticide. The direct implications of such behaviour are that competition can alter individually measured pesticide sorption coefcients. Hydrophobic compounds, such as other pesticides, formulation adjuvants, PAHs, PCBs, can be present in mixed formulations, in treated wastewaters or in sewage sludges from wastewater treatment plants [3841], all of which can reduce the retention of a pesticide by soil and so, facilitate its leaching to groundwaters. In our case dimethoate distribution coefcients, when studied alone, were between 0 and ca. 50% higher than in the presence of the other three insecticides. Cationic surfactants have been proposed to act as barriers for containment of non-ionic organic pollutants [30,42]. Therefore, the sorption coefcients

M.C. Hern ndez-Soriano et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 306 (2007) 4955 a [12] S. Rodrguez-Cruz, M.J. S nchez-Martn, M. S nchez-Camazano, J. Env a a iron. Qual. 33 (2004) 920. [13] C.N. Mulligan, R.N. Yong, B.F. Gibbs, Eng. Geol. 60 (2001) 371. [14] Soil Conservation Service, Soil Survey Laboratory Methods and Procedures for Collecting Samples, USDA, Washington, USA, 1972. [15] M.D. Mingorance, E. Barahona, J. Fern ndez G lvez, in: R. Jim nez a a e Ballesta, A.M. Alvarez Gonz lez (Eds.), II Simposio Nacional del Control a de la Degradaci n de Suelos, Madrid, Spain, 2005, pp. 737741. o [16] E. Barahona, C. Cadaha, M. Casado, M. Chaves, A. G rate, L. Heras, a M. Lachica, M. Lasala, R. Llorca, L. Monta es, M.T. Pardo, V. P rez, L. n e Prat, M. Romero, B. S nchez, Determinaciones analticas en suelos. Nora malizaci n de m todos. IV. Determinaci n de carbonatos totales y caliza o e o activa, in: Proceedings of the I Congreso Nacional de la Ciencia del Suelo, Madrid, Spain, 1984, pp. 5367. [17] L.P. Meier, G. Kahr, Clays Clay Miner. 47 (1999) 386. [18] C.D.S. Tomlin (Ed.), The Pesticide Manual, 13th ed., British Crop Protection Council, Alton, Hampshire, UK, 2003, p. 1344. [19] P. Morrica, F. Barbato, A. Giordano, S. Seccia, F. Ungaro, J. Agric. Food Chem. 48 (2000) 6132. [20] S.Y. Lee, S.J. Kim, S.Y. Chung, C.H. Jeong, Chemosphere 55 (2004) 781. [21] M. Arienzo, T. Crisanto, M.J. S nchez-Martn, M. S nchez-Camazano, J. a a Agric. Food Chem. 42 (1994) 1803. [22] F.C. Spurlock, J.W. Biggar, Environ. Sci. Technol. 28 (1994) 996. [23] J.-F. Lee, M.-H. Hsu, H.-P. Chao, H.-C. Huang, S.-P. Wang, J. Hazard. Mater. B 114 (2004) 123. [24] M.S. Rodrguez-Cruz, M.J. S nchez-Martn, M. S nchez-Camazano, a a Chemosphere 61 (2005) 56.

55

[25] Y.-H. Shen, Chemosphere 41 (2000) 711. [26] I.G. Dubus, E. Barriuso, R. Calvet, Chemosphere 45 (2001) 767. [27] M. S nchez-Camazano, E. Iglesias-Jim nez, M.J. S nchez-Martn, a e a Chemosphere 12 (1997) 3003. [28] M.J. Brown, D.R. Burris, Ground Water 34 (1996) 734. [29] W.C. Koskinen, S.S. Harper, in: H.H. Cheng (Ed.), Pesticides in the Soil Environment: Processes, Impacts and Modeling, Soil Sci. Soc. of America, WI, 1990, pp. 5177 (Book Series No. 2, Chapter 3). [30] J.-F. Lee, J.R. Crum, S.A. Boyd, Environ. Sci. Technol. 23 (1989) 1365. [31] D. Businelli, J. Environ. Qual. 26 (1997) 102. [32] A. Farenhorst, B.T. Bowman, J. Environ. Sci. Health B 33 (1998) 671. [33] J.P. Chen, S.O. Pehkonen, C.-C. Lau, Colloids Surf. A 240 (2004) 55. [34] H.J. Turin, R.S. Bowman, J. Environ. Qual. 26 (1997) 1282. [35] J.A. Smith, P.R. Jaff , Environ. Sci. Technol. 25 (1991) 2054. e [36] G. Sheng, X. Wang, S. Wu, S.A. Boyd, J. Environ. Qual. 27 (1998) 806. [37] W. Zhou, K. Zhu, H. Zhan, M. Jiang, H. Chen, J. Hazard. Mater. B 100 (2003) 209. [38] J.A. Pedersen, M.A. Yeager, I.H. Suffet, J. Agric. Food Chem. 51 (2003) 1360. [39] M. Pardos, C. Benninghoff, L.F. de Alencastro, W. Wildi, Lake Reserv. 9 (2004) 41. [40] S.R. Wild, K.S. Waterhouse, S.P. McGrath, K.C. Jones, Environ. Sci. Technol. 24 (1990) 1706. [41] B. Oldal, E. Maloschik, N. Uzinger, A. Anton, A. Sz k cs, Geoderma 135 e a (2006) 163. [42] G.R. Rakhshandehroo, R.B. Wallace, S.A. Boyd, T.C. Voice, Soil Sci. Soc. Am. J. 62 (1998) 5.