BONATO, P. S.

CERDEIRA, A. L.

GOMES, M. A. F.

LANCHOTE, V. L.

PESSOA, M. C. P. Y.

QUEIROZ, R. C.

UETA, J.

English

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Scientific registration n o : 1130Symposium n o : 7Presentation: posterHerbicides residues in soil and water from sugarcane areain BrazilCERDEIRA Antonio L.(2)  ,LANCHOTE Vera L.  (1),  QUEIROZ Regina C. (1),BONATO  Pierina  S.  (1),GOMES  Marco  Antonio  (2), YOUNG  Conceicão  (2),SHUHAMA Ilda (1), UETA Julieta (1).(1) School of Pharmaceutical Sciences at  Ribeirão Preto  -  USP, 14040-903 RibeirãoPreto, SP - Brazil(2) CNPMA/EMBRAPA, Jaguariúna, SP - BrazilINTRODUCTIONHarmful insects, mites, infectious fungi, bacteria and invasive weeds havebeen controlled by pesticides and herbicides involving a huge world market of more than20 billions dollars annually (10). The practice of long-term, sometimes indiscriminate andabusive use of herbicides in the agriculture and the high persistence of some of themhave been crucial points on the environmental contamination, mainly of groundwater,causing  problems of  water  quality. The  evaluation  of  these  impacts  is  difficult  andexpensive because demands high standard analytical equipment and qualified personnel.The region of Ribeirão Preto city, (São Paulo State) located in Southeastof Brazil is one of the most important  sugarcane producing area,  with high levels ofagrochemicals utilization. This region is also an important recharge area for groundwatersupply for the Botucatu aquifer which comprises areas of eight Brazilian states plus partsof Argentina,  Uruguay and Paraguay, with approximately 1,200,000 Km2.  Geologicalstudies have identified a watershed, Espraiado, as a good research area selecting it as amodel for studies of water and agrochemicals movement toward groundwater.A previous study, made in 1994, by the Institute of Agricultural Economy(IEA, São Paulo) has defined 16 production units in the Espraiado watershed involvingsugarcane,  pasture  for  cattle,  coffee plantation,  and small properties  with diversifiedcrops.  However,  this  diversification  is  not  representative  since  sugarcane  plantationoccupies  about  80%  of  the  total  area  of  the  watershed.  The  information  on  theagricultural practices and herbicides utilization were collected through a farm survey. Thefollowing herbicides  have  been  identified  as  the  most  commonly used  in the  area:atrazine, simazine, ametryne, tebuthiuron, diuron, 2,4-D, and picloran.MATERIAL AND METHODSThe  sampling  criteria  of  soil,  surface,  and  groundwater  of  the  Espraiadowatershed  were  based  on  superposition  of  geological  maps  of  soil  types,  hydraulicconductivity, slope, infiltration, and runoff potentials.SOIL CHARACTERIZATIONSoil samples from nine selected points of the Espraiado watershed (Fig 1)werecharacterized by the determination of the sand, clay and silt content and texture weredefined as shown in Table 1. The sampled soils were classified as Clay, Loam, Sandloamand Sandy, according to Oliveira et al, 1992(5).Figure 1. Espraiado watershed area showing the blue, green, and yellow areas as Sandy andSandloam soils which are more susceptible to herbicide infiltration.Table 1. Texture composition of different samplings points of the area.POINT Sand Sand (fine) Clay Silte Soil Class0-20 80-90 0-20 80-90 0-20 80-90 0-20 80-90 0-20 80-90P04 4.4 2.33 11.0 8.3 56.5 67.3 28.1 22.1 ClayP06 4.4 3.88 14.3 15.59 58.7 60.9 22.5 19.6 ClayP26 5.0 3.39 13.4 12.42 61.5 62.8 20.1 21.4 ClayP20 14.3 13.9 27.7 31.33 10.3 45.1 47.6 9.57 LoamP27 24.3 22.3 62.3 68.83 2.35 7.10 11.5 1.72 SandyP33 41.6 35.2 42.9 46.87 10.8 14.5 4.70 3.48 Sand loamP35 29.3 26.5 65.0 68.33 2.40 2.65 3.30 2.50 SandyP23 46.1 48.6 34.1 39.49 4.20 9.70 15.6 2.21 Sand loamP24 56.4 45.7 35.2 42.26 7.25 9.70 3.15 2.34 SandyHERBICIDES DETERMINATION IN WATER.Surface water  samples (1L)  were  collected  from Espraiado  watershedduring the period from January to July 1996 from different points. Groundwater sampleswere collected from the sites near the river during the same period. For the herbicidesdetermination 100 mL of the water samples were initially filtered under vacuum througha membrane of 0.22u porosity. The filtrates were extracted with 12 mL dichloromethaneand mechanical shaking for one hour (1,2,3).After phase separation, 6 mL of the organic phases were transferred toconic test tubes and evaporated to dryness under nitrogen at 35C. The residues weredissolved in 200  L of  the  mobile phase  and  100  L were  chromatographed  on  aLichrospher  100  RP-8  column (particle  5  m, 125  x 4  mm, Merck)  using 0.05  Mphosphate  buffer, pH 5.5,  and acetonitrile (73:27,  v/v) as mobile phase.  The triazineherbicides were detected at 220 nm, whereas tebuthiuron and diuron were detected at254 nm.(4,7,8,9).  The recovery obtained in the extraction procedure was higher than95% for all herbicides except simazine for which the recovery was 85.6%. Due to theenrichment in the extraction procedure and the sensitive detection at two wavelengths itwas possible to obtain a quantification limit of 0.02 g/L for the herbicides studied. Themethod was linear over the range of 0.02 to 2.0 g/L.HERBICIDES DETERMINATION IN SOILS.Soil samples were grounded and passed through a 2mm sieve to  obtainparticles between 120 - 270 mesh. Five grams aliquots were extracted with 10 mL 1mMNaOH + 20mL ethylacetate for 30 min in ultrasound bath, followed by 16h in waterbathat 500C with stirring (100 cpm). Organic phases were transferred to tubes, centrifugedduring  5  min a  1800xg,  and  10mL of  ethylacetate  fraction  evaporated  to  dryness.Residues suspended in 1.1mL in water were submitted to purification in Supelclean envi-18 columns. Herbicides were eluted with 500uL methanol: ethanol (1:1),  v/v. 100uLwere applied to a liquid chromatograph. RESULTS AND DISCUSSIONThe analyses, in laboratory experiments, have shown the Clay (“Latossoloroxo”, “Latossolo” dark red), Sandloam, and Loam soils presented medium infiltrationpotential of water as opposed to Sandy soil which showed a high infiltration potential.(Table 2), as expected. The Sandy soil, showed as blue area in Fig. 1, is located at thearea of least declivity in the watershed making it much more susceptible for infiltration.Table 2.  Infiltration potentials and runoff of different types of soils of the Espraiadowatershed.Soil Type HydraulicconductivitySlope WaterinfiltrationpotentialRunoffpotentialLatossolo roxo (Clay)High High Medium MediumTerra RoxaEstruturada (Clay)High High Medium MediumLatossolo DarkYellow (Loam)Medium Slight Medium MediumLatossolo Red Yellow(Sandloam)Medium Slight Medium MediumAreia Quartzosa(Sandy)High Slight High LowThe  pH  determination  of  thesoil  samples  revealed  acidic  pH,  except  in  thepoint  designated  P04,  classified  as  Clay  and“latossolo roxo” A significant seasonal variationof around 2 units was observed, with drop of pHin July samples as illustrated in the Figure 3 withsamples  from  points  P06,  P33  and  P35.  Ingeneral  clay samples were more acidic than  thesandy one (P35).  The pH of the  80-90 cm soilsamples were usually ( 6 out of 9) more acidicthan the surface samples (6).Figure 3 - pH values of soil surface samples frompoints P06, P33, and P35.pH44,555,566,57FEBMARAPRMAYJUNJULAUGSEPOCTNOVJANMonthpHP06P33P35The  determination  of  humidity  has  shownresults compatible with those published in theliterature.  Figure  4  shows  the  seasonalvariation of humidity of 3 samples (P06, P33,and  P35).  The  clay  point  has  revealed  avariation from 17 to 34% water content (g/drysoil),  while  the  points  P33  and  P35  anoscillation between 2.3 to 12% humidity. Thelower values coincided with the dry and winterseason of this region (6).   Figure 4 - Humidity  variation  as  observed   with samples from points P06, P33 and P35.The studies with simulation analysis of the herbicides with soil types of the Espraiadowatershed showed the compounds hexazinone,  atrazine,  and tebuthiuron  had the highest  potential  ofreaching the groundwater level.(Table 3).Table 3.  Results obtained  by mathematical  simulation  with  CMLS 94 model for different  herbicidesduring four years.HERBICIDE SOIL TYPE DEPTH (m) AMOUNT(Kg/ha)Hexazinone Sandy 30.0 3.7 X 10-5Latossolo Dark Red (Clay) 7.3 3.7 X 10-5Latossolo Roxo (Clay) 4.7 3.7 X 10-5Diuron Sandy 4.9 1.5 X 10-4Latossolo Dark Red (Clay) 0.77 1.5 X 10-4Latossolo Roxo (Clay) 0.55 1.5 X 10-4Atrazine Sandy 20.5 5.5 X 10-6Latossolo Dark Red (Clay) 4.7 5.5 X 10-6Latossolo Roxo (Clay) 3.1 5.5 X 10-6Ametryne Sandy 8.0 4.1 X 10-6Latossolo Dark Red (Clay) 1.5 4.1 X 10-6Latossolo Roxo (Clay) 0.99 4.1 X 10-6Tebuthiuron Sandy 10.7 3.5 X 10-6Latossolo Dark Red (Clay) 4.6 3.5 X 10-6Latossolo Roxo (Clay) 2.1 3.5 X 10-6Table 4.   Average concentrations of herbicides  g/L at  surface water  samples at  ninepoints of Espraiado ridge during the months of January, February, May, andJuly, 1996.HUMIDITY05101520253035FEBMARAPRMAYJUNJULAUGSEPOCTNOVJANMonth%water/g dry soilP06P33P35POINT MONTH HERBICIDESTebuthiuron Diuron Simazine Atrazine Ametryne01 January n.d. 0,05 n.d. n.d. 0,06February 0,04 n.d. n.d. n.d. n.d.May n.d. n.d. n.d. n.d. n.d.July n.d. n.d. 0,02 n.d. n.d.02 January n.d. 0,06 n.d. n.d. 0,06February 0,04 n.d. n.d. n.d. n.d.May n.d. n.d. n.d. n.do n.d.July n.d. n.d. 0,08 n.d. n.d.03 January 0,02 0,07 n.d. n.d. 0,08February 0,02 0,02 n.d. n.d. 0,03May n.d. n.d. n.d. n.d. n.d.July 0,06 n.d. 0,09 n.d. n.d.04 January n.d. 0,07 n.d. n.d. 0,06February n.d. 0,04 n.d. n.d. 0,03May n.d. n.d. n.d. n.d. n.d.July n.d. n.d. n.d. n.d. n.d.05 January n.d. 0,06 n.d. n.d. 0,05February n.d. 0,04 n.d. n.d. 0,03May n.d. n.d. n.d. n.d. 0,02July 0,07 n.d. 0,03 n.d. n.d.06 January n.d. n.d. n.d. n.d. n.d.February n.d. n.d. n.d. n.d. 0,03May 0,03 n.d. n.d. n.d. 0,05July 0,05 n.d. n.d. n.d. n.d.07 January 0,02 0,06 n.d. n.d. 0,08February 0,03 0,09 n.d. n.d. 0,05May 0,04 0,04 n.d. n.d. 0,03July 0,05 n.d. n.d. n.d. n.d.08 January n.d. n.d. n.d. n.d. n.d.February n.d. 0,02 n.d. 0,03 0,03May 0,03 n.d. n.d. n.d. 0,02July 0,04 n.d. n.d. 0,04 n.d.09 January 0,05 0,21 n.d. n.d. 0,13February n.d. 0,07 n.d. n.d. 0,06May 0,02 0,04 n.d. n.d. 0,06July 0,03 n.d. n.d. n.d. n.d.Detection Limit: 0,02 g/L   n.d. = not detected (< 0,02 g/L)Surface  water  samples  were  collected  during  January  to  July  1996.Analysis of tebuthiuron, diuron, atrazine, simazyne and ametryne residues showed nosignificance amount of these products (above the Maximum Allowable Concentration) inthe water  ridge (Table 4),  although in December, 1995,  only two  out  of nine pointspresented ametryne concentrations above (0.17 and 0.23) the allowable 0.1 ug/L.REFERENCES1.BALINOVA,  A.  Solid-phase  extraction  followed  by  high-performance  liquidchromatographic analysis for monitoring herbicides in drinking water.  Journal ofChromatography, v. 643, p. 203-7, 1993.2.COQUART,  V.,  HENNION,  M.C.  Determination  of  chlorotriazines  in  aqueousenvironmental  samples  at  the  ng/L  level  using  preconcentration  with  a  cationexchanger  and  on-line  high-performance  liquid  chromatography.  Journal  ofChromatography, v. 585, p. 67-73, 1991.3.DURAND,  G.,  BOUVOT,  V.,  BARCELÓ,  D.   Determination  of  trace  levels  ofherbicides  in  estuarine  waters  by  gas  and  liquid  chromatographic  techniques.Journal of Chromatography, v. 607, p. 319-27, 1992.4.LYDON, J.,  ENGELKE, B.F.,  HELLING, C.S.  Simplified high-performance liquidchromatography  method  for  the  simultaneous  analysis  of  tebuthiuron  andhexazinone. Journal of Chromatography, v. 536, p. 223-8, 1991.5.OLIVEIRA, J.B; JACOMINE, P.K.T; CAMARGO, M.N. Classes gerais de solos doBrasil:  guia  auxiliar  para  seu  reconhecimento.  2aedicao.  Jaboticabal,  FUNEP,  1992.201p6.ROCHA,A ., COSTA, F.M., SHUHAMA, I.K., GOMES, M A ., CEDEIRA, A . L.,UETA, J. Variação sazonal de matéria orgânica, umidade e pH em área de cana deaçúcar. Annals of the Congresso Brasileiro de Solos, 1997,  Rio de Janeiro, Brasil(CDRom), to be published elsewhere7.SAUNDERS,  D.G.,  VANATTA,  L.E.   Derivatization  and  gas  chromatographicmeasurement of some thermally unstable ureas. Analytical Chemistry, v. 46, n. 9, p.1319-21, 1974.  8.SCHLETT,  C.  Multi-residue  analysis  of  pesticides  by  HPLC  after  solid  phaseextraction. Fresenius J Anal Chem, v. 339, p. 344-7, 1991.9.STAN, H.J.,  KLAFFENBACH, P.  Determination of carbamate pesticides and someurea pesticides after  derivatization with acetic anhydride by means of GC-MSD.Fresenius J Anal Chem, v. 339, p. 151-7, 1991.10.TANAKA, Y., OMURA, S. Agroactive compounds of microbial origin.  Annu. Rev.Microbiol. 47:57-87. 1993

Herbicides residues in soil and water from sugarcane area in Brazil.

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Herbicides residues in soil and water from sugarcane area in Brazil.

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