in presenceof32mgkg and half-lives of0.8and 80mg kg tebuconazole, tribenuron-methyl. Key words: of TBM wasobviouslyinhibitedinpresenceof TEB. notaffectedTEB was by TBM. However, theadsorption than TBM. When usedcombined, adsorption capacityof higher significantly was TEB of affinity adsorption Soil 18.2% innon-sterilizedandsterilizedsoils, respectively. and 80mgkg microorganisms. Inthenon-sterilized soil,half-livesof0.8 of TEB was markedly affected byconcentration and soil soils whentheywereappliedindividually. The degradation has longerhalf-livescomparedwith TBM inthetested spectrometry (UHPLC-MS/MS).Results showedthat TEB high-performance liquid chromatography tandem mass efficient, rugged and safe method (QuEChERS) with ultra- TBM in soil were determined using a quick, easy, cheap, (pH 7.28)werestudied. The concentrationsof TEB and (TBM) aloneandcombinedapplicationinwheatsoil oftebuconazole(TEB)andtribenuron-methylbehaviors adsorption insoil. Thus, thedegradationandadsorption of apesticideintheenvironmentisitsdegradationand the mostimportantprocessesinfluencingbehavior to acoexistenceofpesticidemixturesinsoil.One or one after another for crop protection. This often leads In practice,pesticidesareusuallysimultaneouslyapplied ABSTRACT TEB alone,theratesofdegradation80mgkg to Compared TEB. of degradation the reduce could TBM of TBM was not affected by TEB in both soils; however, 73.5 dinthe sterilized soil, respectively. The degradation doi:10.4067/S0718-58392017000300281 Accepted: 1 August 2017. Received: 24 April 2017. * Medicine, 266109,Qingdao,China. 2 Pharmaceutical Sciences,266109,Qingdao,China. 1 Feifei Wang wheat soil,aloneandincombination tebuconazole andtribenuron-methyl in Degradation andadsorptionof iga Arclua Uiest, olg o Pat elh and Health Corresponding author([email protected]). Plant of and College University, Chemistry Agricultural of Qingdao College University, Agricultural Qingdao CHILEAN JOURNAL OF AGRICULTURAL RESEARCH 77(3)JULY Adsorption, combined pollution, degradation, -1 1 TEB were16.4and69.3d,respectively, , ZhiWang -1 TBM werereduced15.9%and CHILEAN JOURNAL OF AGRICULTURAL RESEARCH 77(3)JULY 1 , BaohuaZhang -1 TEB were 20.4and 1 , andQingmingZhang -1 TEB - SEPTEMBER 2017 and groundwater hasbeenattracting extensive concern (Kotoula- low dosage,ithighphytotoxicity andpotentialpollutiontosoil worldwide. Although TBM isregardedtobehighlyefficient at sulfonylurea herbicide and is widely usedforcontrolling weed 1,3,5-triazin-2-yl(methyl)carbamoylsulfamoyl]benzoate] isa Tribenuron-methyl (TBM)[methyl2-[4-methoxy-6-methyl- et al.,2004;Komárek2010;Muñoz-Leoz 2011). (Strickland environment ecological soil to risk a posing thus other waysandhasarelativelongerhalf-life(49-610 d), and studies havedemonstratedthat TEB canreachsoilbyfallingor and foliarfungalpathogensinmanycropplants.Previous triazole fungicide,whichiswidelyusedtocontrol soil-borne 3-(1 behaviors ofindividualpesticidesandcombineduseinsoil. in soil. Therefore, it is necessary to compare and analyze the but metribuzin did not affect the behavior of pendimethalin pendimethalin, herbicide of degradation the inhibit significantly fungicide mancozeb andmixture with thiamethoxam could that demonstrated (2012) Gregorczyk and Swarcewicz times. herbicide metolachlorinsoil,andinhibitionrateisuptotwo chlorothalonil could significantly suppress the degradation of given soil. For example, White et al. (2010) foundthat fungicide individual pesticide may be different from other pesticides in a physical-chemical properties,degradationandadsorption of pesticide of difference the to Due 2010). al., et Liu 2002; Swift, and (Spark properties pesticide and constituents soil of adsorption aregoverned byseveral factors such asdifferences and degradation that showed Studies 2008). al., et (Arias-Estévez the soilandhowseriouslypesticideaffect soilenvironment which are directly related to howlongthe pesticides remain in and adsorptionaretwoimportant behaviors ofpesticides in soil, Degradation 2012). Gregorczyk, and (Swarcewicz environment in acombinedcontaminationofpesticideresiduesthesoil the cropfromdamage. This pesticide application can oftenresult usually applied simultaneously or one after another for protecting environment effect. However, inpractice, different pesticidesare on the environmental fate of single pesticide compound and its abuse ofpesticides. At present,moststudiesmainlyhavefocused as waterandsoilpollutionoccurredduetohighfrequencyor insect pest, and weeds. However, environmental problems such tocontroldifferent way of anindispensable typesofdisease, In agricultural production, pesticides application has been one INTRODUCTION Tebuconazole (TEB) [( H -1,2,4-triazol-1-ylmethyl)pentan-3-ol] is a broad-spectrum 2* - SEPTEMBER 2017 RS )-1- p -chlorophenyl-4,4-dimethyl-

281 RESEARCHRESEARCH dose levels were applied: a low dose (0.8 mg TEB kg TEB mg (0.8 dose low a applied: were levels dose pesticide application.Inindividual pesticidepollution,two was immediately transferred to an aseptic chamber prior to for 30 min. In order to maintain soil sterility, the sterile soil °C 120 at autoclaving by sterilized was Soil soil. sterilized non- and soil sterilized substrates: different two in studied was combined and alone TBM and TEB of Degradation Degradation studies until preparationofthecontamination. activity biological maintaining for moisture keep to °C 4 at dried overnight and sieved to passa2-mm mesh, andstored capacity, andpH7.28. The collected soilwaspartiallyair- had 3.75%organic matter, 13.28cmolkg as clayloam(57%sand,23%silt,and20%clay). This soil and TBM applicationinthe past 5yr. Itwascharacterized Agricultural University, an area with no history of TEB Qingdao of park technology agricultural modern at field before using. °C 4 at stored were solutions the of All solution. stock the solutions werefreshlypreparedbyappropriate dilution of prepared in acetonitrile, and the required working standard CHILEAN JOURNAL OF AGRICULTURAL RESEARCH 77(3)JULY standard solutions of1000mg L Stock USA). Missouri, Louis, St. (Sigma-Aldrich, Supelco from purchased were μm) 40-60 (GCB, black carbon graphitized and μm) 40-60 (PSA, amine secondary Primary China). (Tianjin, Reagent YongdaTianjinChemical from areofanalyticalgradeandpurchased sulfate magnesium anhydrous and chloride sodium Acetone, China). (Tianjin, TechnologyConcord Tianjin from purchased were grade) (HPLC methanol and Acetonitrile China). Shandong, provided bytheJingbo Agrochemicals Technology (Boxing, Tebuconazole (98%purity)and TBM (96.5%purity)were Pesticides, reagents, andsoil MATERIALS ANDMETHODS Mehdizadeh etal.,2016). Wheat ( 2010; al., et Olszyk 2000; al., et Battaglin 1993; al., et Syka 0.32 mg TBM kg between twopesticidesinagivenwheatsoil. TBM aloneandcombined,tocomparethedifferences to investigate degradation and adsorption of TEB and in agivenwheatsoil. the degradation and adsorption of TEB and TBM coexisted of years. However, no other studies are available regarding and soilhavebeenwidelyinvestigatedinpreviouscouple Besides, thedissipationstudiesof TEB and TBM inwheat weeds (Homdork et al., 2000; Mukherjee et al., 2015). and theyplayanimportant role incontrolling diseases and field, wheat in pesticides used commonly two are TBM and has been animportant wayto improve wheat yield. TEB population. To overcome this problem, pesticide application and qualityisverycrucialtomeetwiththeincreasing one ofthemostimportantfoodcropsworldwide,itsyield The soil(top0-15cm)usedwascollected from awheat Therefore, the objective ofthe present experiment was -1 ) representsthe recommendeddosage, Triticum aestivum -1 TEB and TBM wereand TBM TEB -1 cation exchange - SEPTEMBER 2017 L.)is -1 and kg and ahighdose(80mg TEB kg kg concentrations of TEB and TBM weresetas2.5mgkg According to the result ofpreliminary experiment, Adsorption study analysis. until °C -20 at stored then and d 90 and 60, 30, 21, 14, 7, 3, (5 g)wererandomlyremovedfromeachtreatment on 0,1, Subsamples capacity.water-holding of 40% to adjusted dark, andthemoisture content ofeach soil sample was were prepared. All samples were incubated at 25°Cinthe polypropylene sheets. Three replicate samples per treatment to a200-mL brownglassbottleandcoveredwithperforated transferred were g) (100 samples soil Spiked (2016). al. et performed accordingtothemethod describedby Wang combined pollution. The mixingofpesticideandsoilwas kg represents a spillage situation. Four treatments (0.8 mg TEB the sameasdescribed abovefordegradation experiment. mL PTFEcentrifugetubeandtherestof steps were experiment, a 3-mL suspension was transferred to a 10 adsorption For analysis. (UHPLC-MS/MS) spectrometry high-performance liquidchromatography-tandem mass ultra- for filter membrane pore μm 0.22 a with vial supernatant wasfilteredintoa1.5mL glassautosampler centrifuged at4000rpmfor10min. An aliquotof1mL firstly vortexedforapproximately 1min,and then anhydrous, and200mgsodiumchloride. The tubewas sulfate magnesium mg 1000 GCB, mg 20 PSA, mg 30 transferred toa10mL PTFEcentrifuge tubecontaining for 10min. The 3-mL acetonitrile supernatant was highest speedfollowedbycentrifugationat4000rpm sample tube. The tube was then vortexed for 2 min at mg magnesium sulfate anhydrous was added into the was vortexedfor2minathighestspeed,andthen1000 then 5mL acetonitrilewereaddedintoit. The sample polytetrafluoroethylene (PTFE)centrifugetube,and experiment, 2gsoilwereweighedintotoa10mL TEB and TBM inthesoil.Briefly, fordegradation separate and extract to used was (QuEChERS) method The quick,easy, cheap,efficient, rugged, and safe Pesticide residue determination further purification. 4000 rpmfor10min,andthesuspensionswereremoved in triplicate. After shaking, thetubeswerecentrifugedat respectively). All adsorption experiments were conducted different periods oftime (0.5,1,2,3,4,12,16,20,24h, over agitated and °C 25 to controlled shaker orbiter an in 5 gsoilin50mL ofcentrifuge tubes. The tubeswereplaced chloride. Ten milliliters of pesticide solution were added to 2000). All pesticides were dissolved in a 0.01 M calcium (No, guideline (OECD) Development and Co-operation equilibration method refer to Organization forEconomic batch thestandard performedusing The procedurewas -1 -1 -1 +32mg TBM kg , 80mg TEB kg + 0.32 mg TBM kg -1 +0.32mg TBM kg -1 ) werestudiedinthetwopesticides -1 , 0.8 mg TEB kg -1 and32mg TBM kg -1 , and80mg TEB -1 + 32 mg TBM -1 -1 ) .

282 k, where C where k, methyl (TBM)insoil. Table 1.Recoveries of tebuconazole(TEB)andtribenuron- CHILEAN JOURNAL OF AGRICULTURAL RESEARCH 77(3)JULY mgkg min L 8.0 with °C 350 was gas of temperature Nitrogen wasusedforbothnebulizerandcollisiongas. The source. (ESI) ionization electrospray an with mode (MRM) was operated in positive multiple reaction monitoring and run time was 5.5 min.detectionspectrometric Mass μL 5 was volume injection The v/v). (60:40, acid formic aqueous methanol:0.1% was phase mobile The °C. 35 at maintained μm) 2.7 × mm 2.1 × mm (75 column EC-C18 TEB and TBM wasachievedonan Agilent Poroshell120 of separation The USA). California, Clara, Santa (Agilent, instrument UHPLC/MS/MS Infinity/6460 1290 Agilent an 0.001 and0.005mgkg were pesticides two of (LOQs) quantification of limits and (LODs) detection of limits The method. the of repeatability 2.6% ~6.4%,respectively, indicatinggoodaccuracyand 96.3% withrelative standarddeviationsof0.4%~8.5%and and sterilizedsoilswere80.8%~87.2%85.2% average recoveries of TEB and TBM from non-sterilized in shown As Table 1,foralllevelsofconcentration,the in terms of recoveries of TEB and TBM spiked in soils. The validationoftheextractionmethodwasevaluated Validation ofpesticideresidue analysismethod RESULTS ANDDISCUSSION TEB and TBM residue. and determinationmethodissatisfactoryforanalysis of extraction the that indicated data These respectively. 10:1, Average ofthree replicates.RSD:Relativestandard deviation. TBM TEB equation. Moreover, the equations (C equations the Moreover, equation. two pesticides was fitted to first-order exponential decay treatments atasamesamplingtime. The degradationof t-test ( one-way ANOVA.using analyzed were Dunnett’sdata The software (IBMCorporation, Armonk, New York, USA). All SPSS18.0 using performed was analysis Statistical Statistical analysis TEB and TBM were2.85and2.24min,respectively. of times retention respectively.The TBM, for 155.2 m/z and 396.2 m/z TEB, for 70.2 m/z and 308 m/z were ions and the nebulizing gas pressurewas 25 psi. The monitored constant andhalf-life. is thehalf-life)wereusedtocalculatedegradationrate is theinitialconcentration,krateconstant,andt Pesticide The concentrationsof TEB and TBM weredeterminedby P < 0.05)wasusedtocomparedifferences between Fortified t is the concentration of pesticide at time t, C t, time at pesticide of concentration the is level 32.0 80.0 0.32 0.8 -1 % recovery Average -1 Non-sterilized soil 84.5 80.8 83.5 87.2 at signal-to-noise ratios of 3:1 and 3:1 of ratios signal-to-noise at RSDs 0.9 8.5 6.7 0.4 % t = C 0 e -kt recovery Average andt 86.3 2.6 85.2 4.2 96.3 4.5 88.6 6.4 Sterilized soil % - -1 SEPTEMBER 2017 flow rate, flow 1/2 = ln2/ = RSDs % 1/2 0

Collecting the lower the Collecting found TBM mineralization not occurred in natural soil. accordance withreports by Andersen et al. (2001), who microorganisms and concentration. This result was in that 2), suggesting TBM degradationisnotaffected by were not obvious changes at both spiked levels (Table In non-sterilized and sterilized soils, the half-lives of TBM 2016). al., et Castillo 2011; al., et Muñoz-Leoz 2009; al., et Sehnem 2004; al., et (Strickland substrates different in degradation of TEB ismediated mainly by microorganisms fact isalsoinlinewithpreviousreports,whichfoundthat indeed playanimportantrolein TEB degradation. This was furtherevidencethatsoilindigenousmicroorganisms sterilized soil wasfaster than sterilized soil (Table 2). This of thepresentstudy, thedegradationrateof TEB innon- degradative activity of soilmicroorganisms. Fromthe result may behigherconcentrationsof TEB couldinhibitthe of highconcentrations TEB insoil. A possiblereason also observedasignificantdecreaseatdegradationrate by Muñoz-Leoz et al. (2011) and Wang et al. (2016), who reports previous with agrees finding present The soil. the in the degradationrateof onitsconcentrationTEB depends water partition coefficient of TEB ( TEB of coefficient partition water al., 2015). couldbeattributedthehigheroctanol- The reason et Dong 2011; al., et Muñoz-Leoz 2004; al., et (Strickland relative long persistence but TBM iseasily degraded in soil those ofprevious reports,which described that TEB hasa threatens to soil ecosystem. The results were consistent with persistent in the soil and has potentially moreserious all thesoilsstudied(Table 2),indicatingthat TEB ismore of longerthanthosefor significantly TEB were TBM in respectively. Among them,half-livesforthedissipation to 86.9dand3.03.9inthesoil(sterilizedornot), lives of TEB and TBM at both dose were ranged from 16.4 the degradation data (Table 2).Forsingle pesticide, half- fitting the linear-order kinetics exponential equationto than thatat0.8mgkg of determination (R determination of coefficient the of values higher the by illustrated was This sterilized soils followed first-order kinetics (Figure 1). and non-sterilized in pesticides two of Degradation application insoil Degradation of TEB and combinedTBM aloneand TEB at 80mgkg bonded withsoil. As shownin Table 1,thehave-lifeof be that TBM haslow sterilized andsoils (Figure1). The reasonmay of bothconcentrations with unaffectedTEB was innon- (Beyer etal.,1987; Andersen etal.,2001). functional group,whichissusceptibletohydrolyticreaction for a mainpathway ithasthe degradationsince TBM previous studies have also confirmed that hydrolysis is Moreover, hydrolysis. chemical of contribution significant with TBM ( TBM with presence of TBM. This suppressionin TEB degradation soil. However, thedegradationof TEB wassuppressedin The rate of TBM dissipation when applied in combination K ow = 0.36), which means means =0.36),which moreeasilyTEB is -1 (above69d)was significantly longer 2 K > 0.84), which was obtained through ow -1 K value,thismaybeattributed to the (about20d). This indicatedthat ow andfasterdegradationrate in K ow = 5000) compared

283 side, half-livesof80mgkg 39.6% comparedto TEB alone,respectively. Ontheother mg kg calculated half-livesof TEB whenappliedin 0.32and32 CHILEAN JOURNAL OF AGRICULTURAL RESEARCH 77(3)JULY (Figure 1). At 0.8mgkg strongerwiththeincreaseof rate was TBM concentration from themean. B) andsterilized soils (CandD).Eachvalueisthemeanofthree replicates, andtheerror bardeviation change depictsstandard Figure 1.Degradationoftebuconazole (TEB) andtribenuron-methyl (TBM)individualandcombinedusedinnon-sterilized (A and presence of0.32and32mgkg pattern of TEB degradation in presence of TBM was same levels, respectively(Table 2).Inthesterilizedsoils, was alsoreduced3.6%and 15.9%atbothconcentration rate degradation alone, TEB with Compared respectively. Table 2. Half-life values (T mgkg 0.8 TEB Different lettersofeachcolumn T 32 TBM +80 TEB 32 TBM +0.8 TEB 32 TBM 0.32 TBM +80 TEB 0.32 TBM +0.8 TEB 0.32 TBM 80 TEB +32 TBM 80 TEB +0.32 TBM 80 TEB 0.8 TEB +32 TBM 0.8 TEB +0.32 TBM (TBM) individualandcombinedusedinsterilizednon-sterilizedsoils. Treatments -1 TBM were18.3and22.9d,increasing11.6% and -1

Regression equation 1/2 C =0.5818e C =26.3540e C =24.2582e C =25.2447e C =0.2484e C =0.2494e C =0.2466e C =64.1583e C =59.4170e C =53.5369e C =0.7551e C =0.6673e -1 -1 ) and other statistical parameters for the degradation of tebuconazole (TEB) and tribenuron-methyl 1/2 TEB were71.8and 80.3din , innon-sterilizedsoil,the -1 representsignificantdifference ( TBM innon-sterilized soil, -0.2299t -0.2165t -0.2242t -0.0302t -0.00379t -0.0423t -0.1802t -0.0086t -0.0097t -0.0100t -0.1904t -0.1862t Non-sterilized soil

- SEPTEMBER 2017 d 0.9854 0.9767 0.9694 0.986 0.8282 0.8733 0.8225 0.9029 0.9109 0.9858 0.9808 0.9521 R 2 P <0.05)atsamepesticideconcentration. be responsible for the decrease in TEB degradation rate. TEB with TBM anditsmetaboliteswerepresumedto Therefore, toxicityandnon-competitive inhibitionof to havelessinfluenceindegradation ofbothpesticides. different mechanisms,competitiveinhibitionisexpected different chemicalstructureandwere degradedinsoilsby combined pollution system. Because TEB and TMB have inhibition, canresultindecreasingdegradationrates in factors, namely toxicity, competitive and non-competitive interactive potential three (1999), Stensel and Bielefeldt of to that in the non-sterilized soil. According to the theory 3.8a 3.0a 3.2a 3.1a 80.3b 71.8a 69.3a 22.9c 16.4a 3.6a 3.7a 18.3b T 1/2 Regression equation

C =25.3998e C =0.2542e C =0.2437e C =0.2522e C =61.1660e C =59.1229e C =53.9424e C =0.7323e C =0.6189e C =26.2498e C =23.9499e C =0.6328e -0.2076t -0.1805t -0.1891t -0.0214t -0.0280t -0.0339t -0.1865t -0.1872t -0.1778t -0.0080t -0.0093t -0.0094t

Sterilized soil d 0.9857 0.9882 0.9856 0.9864 0.9822 0.9801 0.8908 86.9b 0.8476 74.3a 0.8637 73.5a 0.9630 32.3c 0.9521 24.8b 0.9504 20.4a R 2 3.7a 3.7a 3.9a 3.3a 3.8a 3.7a T 1/2

284 CHILEAN JOURNAL OF AGRICULTURAL RESEARCH 77(3)JULY to thedeclineof TBM adsorption.Moreover, inpresence occupied moreadsorptionpointsinthesoil,andthuslead and affinity adsorption higher has TEB that be may reason of TBM decreased in soil involved TEB (Figure 2). The TEB was not affected by TBM, however the adsorption of affinity adsorption soil the use, combined For particles. and would berepelled bythe negatively charged clay is predominantlyintheanionicformsoil(pH7.28), adsorption capacity of TBM should duetothispesticide on theresearchofÁlvarez-Benedíetal.(1998),low is inaccordancewithmentionedpreviousstudies.Based which TBM, than higher significantly was TEB of affinity (Bermúdez-Couso et al., 2011). Inthis study, soil adsorption gradually saturatedandresultedinasloweradsorption the increasingadsorption,soiladsorptionpointswere increasing theadsorptionratesofthesetwopesticides. With thereby process, adsorption the of hours first the in points reason may be that soil surface present many adsorption and followedbyasloweradsorption(Figure2). The showed aninitialfastadsorptioninthefirstfewhours, application single pesticide, in thesoil. For TEB and TBM adsorption variation of TEB and TBM alone and combined out inthepresentstudy. Inhere,weonlyinvestigated the the adsorptionisothermsofbothpesticides was notcarried Papadopoulou etal.,2016). Therefore, theexperimenton 2013; al., et Cadková 1998; al., et Álvarez-Benedí 1993; al., differentadsorption in low a presents (Kotoula-Syka et soils revealed that TEB has a moderate adsorption but TBM different soil environment have been reported. These studies Until now, many studies on adsorption of TEB and TBM in application insoil Adsorption of TEB and TBM aloneandcombined need tobefurtherstudied. still mechanism influence specific the However, herbicides. could causedecreaseofdegradationratestwodifferent et al. (2008), who thought that above mentioned factors This speculation was in line with previous report byLi combined usedinsoil. and tribenuron-methyl (TBM,dashline)individualand Figure 2. Adsorption curveoftebuconazole(TEB,solidline) - SEPTEMBER 2017 deserve furtherstudies. of TEB and TBM combinedpollutionindifferent soilpH behavior adsorption the Thus, 2013). al., et Cadková 1994; (Riise, adsorption TBM and TEB in role crucial a plays pH about neutral).However, previousliterature has pointedthat adsorption behavior of TEB and TBM in one soil (pH 7.28, It shouldbenotedthatourstudyonlyinvestigatedthe TBM mightincreasethethreattogroundwaterresources. environment indicated that combinedpollutionof TEB and of TEB, the decrease of TBM adsorption rate in the soil adsorption capacityof TBM inthesoil. with TEB alone,butthe presence of TEB can decrease the TBM, TEB adsorption affinity did not change compared TEB wassignificantlyhigherthan TBM. Inpresenceof of affinity adsorption Soil soils. both in TBM by inhibited obvious change. However, TEB degradation can be slightly used, TBM degradationinpresenceof TEB wasnotan concentration, sterilizedsoil,thelongerlife).Forcombine role in TEB degradationinthesoil(showinghigher cannot affect TBM degradation, buttheyplayanimportant not) or (sterilized microorganisms soil and Concentration compared with TEB in non-sterilized and sterilized soils. single pesticide,degradationof TBM wasmarkedlyfaster and combinedwerestudiedinwheatsoil.Overall,for alonetebuconazole (TEB)andtribenuron-methyl(TBM) In thisstudy, thedegradationandadsorptionof CONCLUSIONS Battaglin, W., Furlong, E., Burkhardt, M., and Peter, C. 2000. C. Peter, and M., Burkhardt, E., W.,Furlong, Battaglin, E., Martínez-Carballo, E., López-Periago, M., Arias-Estévez, Jacobsen, and R., Bossi, T.,P.B.,Holst Hertz, S.M., Andersen, Sorption 1998. J. Fernández, and A., Cartón, J., Álvarez-Benedí, REFERENCES Qingdao Agricultural University(QYC201520). in graduate for Innovation Scientific of Program the and (ZR2016CM11),Province Shandong of Foundation Science Natural National the (41101488), China of Foundation Science Natural National the by funded was work This ACKNOWLEDGEMENTS Environment 248:123-133. Totalthe of Science 1998. States, United Midwestern the in and otherherbicidesinrivers, reservoirsandgroundwater Occurrence of sulfonylurea, sulfonamide, imidazolinone, Environment 123:247-260. pollution of groundwater resources. Agriculture, Ecosystems & The mobilityanddegradationofpesticidesinsoilsthe 2008. L. García-Río, and J.C., Mejuto, J., Simal-Gándara, Chemosphere 45:775-782. profile. sediment groundwater and soil Danish one in methyl methyl, tribenuron-methyl,chlorsulfuronandthifensulfuron- metsulfuron- C-labelled 14 of studies Mineralisation 2001. C.S. 46:2840-2844. Chemistry Food and Agricultural of Journal soils. by methyl of tribenuron-methyl, chlorsulfuron, and imazamethabenz-

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