Izitshabalalisi kwimisinga ziya zisiba yinkxalabo yehlabathi, kodwa kukho ulwazi oluncinci malunga noxinzelelo olukhuselekileyo lwendalo yasemanzini.Kuvavanyo lweentsuku ezingama-30 lwe-mesocosmic, ii-invertebrates zasemanzini zomthonyama ze-benthic zavezwa kwisibulali-zinambuzane esiqhelekileyo i-fipronil kunye neentlobo ezine zeemveliso zokuthotywa.Ikhompawundi ye-fipronil ibangele utshintsho ekuveleni kunye ne-trophic cascade.I-concentration esebenzayo (EC50) apho i-fipronil kunye ne-sulfide yayo, i-sulfone kunye ne-desulfinyl degradation imveliso ebangela ukuba impendulo ye-50% iphuhliswe.Iirhafu azikhathaleli kwi-fipronil.Uxinzelelo lwengozi ye-5% yeentlobo ezichaphazelekayo ukusuka kumaxabiso ali-15 e-mesocosmic EC50 isetyenziselwa ukuguqula ukuhlangana kwefipronil kwisampulu yesampulu kwisambuku seeyunithi ezinetyhefu (∑TUFipronils).Kwi-16% yemilambo ethathwe kuphononongo lwengingqi oluhlanu, umndilili we-∑TUFipronil udlule kwi-1 (ebonisa ubutyhefu).Izalathi zezilwanyana ezingenamqolo zeentlobo ezisemngciphekweni zinxulunyaniswa kakubi neTUTUipronil kwindawo ezine kwezintlanu zesampulu.Olu vavanyo lomngcipheko we-ikholoji lubonisa ukuba ukugxila okuphantsi kweekhompawundi ze-fipronil kuya kunciphisa iindawo zokuhlala kwiindawo ezininzi zase-United States.
Nangona ukuveliswa kweekhemikhali zokwenziwa kuye kwanda kakhulu kumashumi eminyaka akutshanje, impembelelo yale michiza kwi-ecosystems engajoliswanga kuyo ayizange iqondwe ngokupheleleyo (1).Kumanzi angaphezulu apho i-90% yomhlaba weefama wehlabathi jikelele ilahlekile, akukho datha kwi-pesticides yezolimo, kodwa apho kukho idatha, ixesha le-pesticides ligqithise i-regulatory thresholds lisiqingatha (2).Uhlalutyo lwemeta lwezitshabalalisi zezolimo kumanzi angaphezulu kwamanzi e-United States lufumanise ukuba kwi-70% yeendawo zesampulu, ubuncinci isibulali-zinambuzane esinye sigqithise kumda wolawulo (3).Nangona kunjalo, olu hlalutyo lwe-meta (2, 3) lujolise kuphela kumanzi angaphezulu achaphazelekayo kusetyenziso lomhlaba wezolimo, kwaye isishwankathelo sezifundo ezicacileyo.Amayeza okubulala izitshabalalisi, ingakumbi amayeza okubulala izinambuzane, nawo akhona kwiindawo eziphakamileyo kwimijelo yemibhobho yedolophu (4).Kunqabile ukwenza uhlolo olubanzi lwezitshabalalisi kumanzi angaphezulu akhutshwa kwezolimo kunye nembonakalo yedolophu;ke ngoko, akwaziwa ukuba imichiza yokutshabalalisa izinambuzane ibeka isoyikiso esikhulu kubutyebi bamanzi angaphezulu kunye nemfezeko yabo yendalo.
I-Benzopyrazoles kunye ne-neonicotinoids zibalwe kwisithathu kwimarike ye-pesticide yehlabathi ngo-2010 (5).Kumanzi angaphezulu e-United States, i-fipronil kunye neemveliso zayo zokuthotywa (phenylpyrazoles) zezona zixhaphakileyo ze-pesticide compounds, kwaye ukugxila kwazo ngokuqhelekileyo kudlula imigangatho yamanzi (6-8).Nangona i-neonicotinoids iye yatsala ingqalelo ngenxa yempembelelo yazo kwiinyosi kunye neentaka kunye nokuxhaphaka kwazo (9), i-fipronil inetyhefu ngakumbi kwiintlanzi kunye neentaka (10), ngelixa ezinye i-phenylpyrazoles Iikhompawundi zeKlasi zineempembelelo ze-herbicidal (5).I-Fipronil sisibulala-zinambuzane esicwangcisiweyo esisetyenziselwa ukulawula izinambuzane kwiindawo zasedolophini kunye nezolimo.Ekubeni i-fipronil yangena kwimarike yehlabathi ngo-1993, ukusetyenziswa kwe-fipronil e-United States, eJapan nase-United Kingdom kuye kwanda kakhulu (5).EUnited States, i-fipronil isetyenziselwa ukulawula iimbovane kunye neentubi, kwaye isetyenziselwa izityalo ezibandakanya umbona (kubandakanywa nonyango lwembewu), iitapile kunye nemifuno (11, 12).Ukusetyenziswa kwezolimo kwe-fipronil e-United States kwanda kwi-2002 (13).Nangona kungekho datha yesizwe yokusetyenziswa kwedolophu ekhoyo, ukusetyenziswa kwedolophu eCalifornia kunyuke ngo-2006 nango-2015 (https://calpip.cdpr.ca) .gov/main .cfm, ifikeleleke nge-2 kaDisemba 2019).Nangona ugxininiso oluphezulu lwefipronil (6.41μg/L) lufunyanwa kwimijelo kwezinye iindawo zezolimo ezinamazinga aphezulu okusetyenziswa (14), xa kuthelekiswa nemijelo yezolimo, imijelo yasezidolophini e-United States idla ngokuba nokubonwa okuthe kratya kunye nokugxilwa okuphezulu okuphezulu, okulungileyo ukwenzeka kwezaqhwithi kunxulunyaniswa novavanyo (6, 7, 14-17).
I-Fipronil ingena kwi-ecosystem ye-ecosystem ye-runoff okanye i-leaches ukusuka emhlabeni ukuya kumlambo (7, 14, 18).I-Fipronil ine-volatility ephantsi (umthetho kaHenry i-2.31 × 10-4 Pa m3 mol-1), i-solubility yamanzi ephantsi ukuya kwimodareyitha (3.78 mg / l kwi-20 ° C), kunye ne-hydrophobicity ephakathi (log Kow yi-3.9 ukuya kwi-4.1) ukushukuma komhlaba kuncinci kakhulu (log Koc yi-2.6 ukuya ku-3.1) (12, 19), kwaye ibonisa ukuzingisa okuphantsi ukuya phakathi kokusingqongileyo (20).I-Finazepril ihlaziywa yi-photolysis, i-oxidation, i-pH-exhomekeke kwi-hydrolysis kunye nokunciphisa, ukwenza iimveliso ezine eziphambili zokuthotywa: i-dessulfoxyphenapril (okanye i-sulfoxide), i-phenaprenip sulfone (sulfone), i-Filofenamide (amide) kunye ne-filofenib sulfide (sulfide).Iimveliso zokuthotywa kwe-Fipronil zivame ukuzinza kwaye zihlala ziqinile kunekhompawundi yomzali (21, 22).
Ubuthi be-fipronil kunye nokuthotywa kwayo kwiintlobo ezingajoliswanga (ezifana ne-invertebrates yasemanzini) ibhalwe kakuhle (14, 15).I-Fipronil yikhompawundi ye-neurotoxic ephazamisa ukuhamba kwe-ion ye-chloride ngokusebenzisa umjelo we-chloride olawulwa yi-gamma-aminobutyric acid kwizinambuzane, okukhokelela kugxininiso olwaneleyo lokubangela imincili kunye nokufa (20).I-Fipronil inetyhefu ekhethiweyo, ngoko ke inobudlelwane obubophelelayo be-receptor kwizinambuzane kunezilwanyana ezincancisayo (23).Umsebenzi we-insecticidal weemveliso zokuthotywa kwe-fipronil uhlukile.Ubuthi be-sulfone kunye ne-sulfide kwii-invertebrates zamanzi ahlaziyekileyo bufana okanye buphezulu kunobuxhakaxhaka babazali.I-Desulfinyl inobuthi obuphakathi kodwa ayinayo ityhefu encinci kunekhompawundi yomzali.Ngokuthelekisa non-ityhefu (23, 24).Ukuchaphazeleka kwee-invertebrates zasemanzini kwi-fipronil kunye nokuthotywa kwe-fipronil kuyahluka kakhulu ngaphakathi naphakathi kwe-taxa (15), kwaye kwezinye iimeko kude kudlule umyalelo wobukhulu (25).Okokugqibela, kukho ubungqina bokuba i-phenylpyrazoles inetyhefu ngakumbi kwi-ecosystem kunokuba bekucingelwa ngaphambili (3).
Imilinganiselo yebhayoloji yasemanzini esekwe kuvavanyo lwetyhefu yelabhoratri inokuwujongela phantsi umngcipheko wabantu basendle (26-28).Imigangatho yasemanzini idla ngokusekwa ngovavanyo lwetyhefu lwelabhoratri yodidi olunye kusetyenziswa uhlobo olunye okanye ezininzi zezilwanyana zasemanzini ezingenamqolo (umzekelo, iDiptera: Chironomidae: Chironomus and Crustacea: Daphnia magna and Hyalella azteca).Ezi zilwanyana zovavanyo ngokuqhelekileyo zilula ukuzihlakulela kunezinye i-benthic macroinvertebrates (umzekelo, i-phe genus : :), kwaye kwezinye iimeko azibonakali kangako kwizinto ezingcolisayo.Umzekelo, i-D. Magna ayikhathaleli kakhulu kwiintsimbi ezininzi kunezinambuzane ezithile, ngelixa i-A. zteca ingabonakali kakhulu kwi-pyrethroid insecticide bifenthrin kunovakalelo bayo kwiimbungu (29, 30).Olunye unyino lwemilinganiselo ekhoyo ziingongoma zokuphela ezisetyenziswayo kwizibalo.Iimpawu ezibukhali zisekelwe kukufa (okanye kumiselwe i-crustaceans), ngelixa i-benchmarks ezingapheliyo zihlala zisekelwe kwi-sublethal endpoints (ezifana nokukhula kunye nokuzala) (ukuba kukho).Nangona kunjalo, kukho imiphumo ebanzi ye-sublethal, efana nokukhula, ukuvela, ukukhubazeka, kunye nokulibaziseka kophuhliso, ezinokuchaphazela impumelelo yerhafu kunye noluntu.Ngenxa yoko, nangona ibhentshimark ibonelela ngemvelaphi yokubaluleka kwebhayoloji yesiphumo, ukufaneleka kwe-ikholoji njengomda wetyhefu akuqinisekanga.
Ukuze uqonde ngcono imiphumo ye-fipronil compounds kwi-benthic ecosystems yasemanzini (i-invertebrates kunye ne-algae), uluntu lwendalo lwe-benthic lwangeniswa kwibhubhoratri kwaye lwavezwa kwii-gradients zoxinaniso ngexesha le-30-day flow Fipronil okanye enye yezilingo ezine zokuthotywa kwe-fipronil.Injongo yophando kukuvelisa uhlobo oluthile lwe-50% yempembelelo yoxinaniso (ixabiso le-EC50) kwikhompawundi nganye ye-fipronil emele i-taxa ebanzi yommandla womlambo, kunye nokumisela impembelelo yongcoliseko kulwakhiwo loluntu kunye nomsebenzi [okt, ugxininiso lwengozi] 5 I-% yeentlobo ezichaphazelekayo (HC5) kunye neziphumo ezingathanga ngqo ezifana nokuhluma okutshintshileyo kunye ne-trophic dynamics].Emva koko umda (ixabiso le-HC5 elidityanisiweyo) elifunyenwe kuvavanyo lwe-mesoscopic lasetyenziswa kwibala eliqokelelwe yi-United States Geological Survey (USGS) ukusuka kwimimandla emihlanu yase-United States (kuMntla-mpuma, uMzantsi-mpuma, uMbindi-ntshona, uMntla-ntshona wePasifiki, kunye noMbindi weCalifornia). Ummandla woNxweme) Idatha) njengenxalenye yovavanyo lomgangatho womlambo wengingqi we-USGS (https://webapps.usgs.gov/rsqa/#!/).Ngokokwazi kwethu, olu luvavanyo lokuqala lomngcipheko we-ikholoji.Iphanda ngokubanzi iziphumo zeekhompawundi ze-fipronil kwizinto eziphilayo ze-benthic kwindawo elawulwayo ye-meso, kwaye emva koko isebenzise ezi ziphumo kwiimvavanyo zommandla welizwekazi.
Uvavanyo lweentsuku ezingama-30 lwe-mesocosmic lwenziwa kwi-USGS Aquatic Laboratory (AXL) eFort Collins, eColorado, eU.SA ukusuka ngo-Oktobha 18 ukuya kwi-17 kaNovemba ka-2017, ngosuku olu-1 lokwenziwa ekhaya kunye neentsuku ze-30 zokulinga.Indlela iye yachazwa ngaphambili (29, 31) kwaye icacisiwe kwimathiriyeli eyongezelelweyo.Ulungiselelo lwesithuba se-meso luqulathe ukuhamba okujikelezayo okungama-36 kuqukuqelo olune olusebenzayo (iitanki zamanzi ezijikelezayo).Umjelo ngamnye ophilayo uxhotyiswe nge-cooler yokugcina ubushushu bamanzi kwaye ukhanyiswa ngomjikelezo we-16: 8 wokukhanya-ubumnyama.I-meso-level flow flow is stainless steel, efanelekile kwi-hydrophobicity ye-fipronil (log Kow = 4.0) kwaye ifanelekile kwi-solvents yokucoca i-organic (Figure S1).Amanzi asetyenziselwa umfuniselo we-meso-scale aqokelelwa kuMlambo iCache La Poudre (imithombo yomlambo ephezulu equka iRocky Mountain National Park, iHlathi leSizwe kunye neContinental Divide) kwaye agcinwa kwiitanki zokugcina ezine ze-polyethylene ze-AXL.Uvavanyo lwangaphambili lwentlenga kunye neisampulu zamanzi eziqokelelwe kwisiza azizange zifumane naziphi na izibulala-zinambuzane (29).
Uyilo lovavanyo lwe-meso-scale lubandakanya i-30 processing streams kunye ne-6 control streams.Umlambo wonyango ufumana amanzi ahlambulukileyo, ngalinye liqulethe ukugxininiswa okungapheliyo kwe-fipronil compounds: i-fipronil (i-fipronil (i-Sigma-Aldrich, i-CAS 120068-37-3), i-amide (i-Sigma-Aldrich, i-CAS 205650-69-7), iqela le-desulfurization [I-Arhente yokuKhuselwa kokusiNgqongileyo yase-US (EPA) iThala leencwadi le-Pesticide, i-CAS 205650-65-3], i-sulfone (i-Sigma-Aldrich, i-CAS 120068-37-2) kunye ne-sulfide (i-Sigma-Aldrich, i-CAS 120067-83-6); 97.8%. Ngokwemilinganiselo yempendulo epapashiweyo (7, 15, 16, 18, 21, 23, 25, 32, 33) Ngokunyibilikisa i-fipronil kwi-methanol (i-Thermo Fisher Scientific, inqanaba lesiqinisekiso se-American Chemical Society), kunye ne-dilute. ngamanzi e-deionized ukuya kumthamo ofunekayo ukulungiselela isisombululo se-stock concentrated ngenxa yokuba inani le-methanol kwi-dose lihlukile, kuyimfuneko yokongeza i-methanol kuyo yonke imifudlana yonyango njengoko kuyimfuneko, ukuqinisekisa ukugxilwa kwe-methanol efanayo. I-0.05 ml / L) kwimifudlana ephakathi kweminye imijelo yokulawula emithathu ifumene amanzi omlambo ngaphandle kwe-methanol, ngaphandle koko baphathwa njengeminye imijelo.
Ngomhla we-8, umhla we-16 kunye nomhla wama-26, ubushushu, ixabiso le-pH, ukuhanjiswa kombane kunye nokuthotywa kwe-fipronil kunye ne-fipronil kulinganiswe kwi-membrane yokuhamba.Ukuze ulandelele ukuthotywa kwe-fipronil yekhompawundi yomzali ngexesha lovavanyo lweendaba, i-fipronil (abazali) yayisetyenziselwa ukunyanga i-mucosa yamathumbu e-intestinal ezinye iintsuku ezintathu [iintsuku 5, 12 kunye ne-21 (n = 6)] kwiqondo lokushisa, pH , I-Conductivity, i-fipronil kunye ne-fipronil degradation isampuli.Iisampulu zohlalutyo lwe-pesticide ziqokelelwe ngokuhluza i-10 ml yamanzi aqukuqelayo kwi-20 ml yeglasi yeglasi yeglasi nge-Whatman 0.7-μm GF / F yesirinji yokucoca enenaliti enkulu yobubanzi.Iisampulu zaqaliswa ngoko nangoko kwaye zathunyelwa kwi-USGS National Water Quality Laboratory (NWQL) eLakewood, eColorado, eU.SA ukuze ihlalutywe.Ukusebenzisa indlela ephuculweyo yendlela epapashiweyo ngaphambili, iFipronil kunye neemveliso ze-4 zokuthotywa kweisampulu zamanzi zagqitywa ngesitofu esithe ngqo se-aqueous (DAI) liquid chromatography-tandem mass spectrometry (LC-MS / MS; Agilent 6495).Inqanaba lokufumanisa isixhobo (i-IDL) liqikelelwa ukuba ngowona mgangatho usezantsi wokulinganisa ohlangabezana nomgangatho wokuchongwa;i-IDL ye-fipronil yi-0.005 μg/L, kunye ne-IDL yezinye ezine fipronil yi-0.001 μg/L.Izinto ezongezelelweyo zibonelela ngenkcazo epheleleyo yeendlela ezisetyenziselwa ukulinganisa i-fipronil compounds, kubandakanywa nokulawula umgangatho kunye neenkqubo zokuqinisekisa (umzekelo, ukubuyiswa kwesampuli, i-spikes, ukuhlolwa komntu wesithathu, kunye neendawo ezingenanto).
Ekupheleni kovavanyo lwe-30-day Mesocosmic, ukubalwa kunye nokuchongwa kwabantu abadala kunye ne-larval invertebrates kwagqitywa (isiphelo sokuqokelela idatha).Abantu abadala abasakhulayo baqokelelwa kumnatha yonke imihla kwaye bafakwe kwi-15 ml ye-Falcon centrifuge ecocekileyo.Ekupheleni kovavanyo (usuku lwe-30), iziqulatho ze-membrane kumlambo ngamnye zaxutywa ukuze zisuse nayiphi na i-invertebrates, kunye ne-sieved (250 μm) kwaye igcinwe kwi-80% ye-ethanol.I-Timberline Aquatics (i-Fort Collins, i-CO) igqibe ukuchongwa kwe-taxonomic ye-larvae kunye ne-invertebrates yabantu abadala ukuya kwinqanaba eliphantsi le-taxonomic elinokwenzeka, ngokuqhelekileyo iintlobo.Ngeentsuku ze-9, 19 kunye ne-29, i-chlorophyll a yayilinganiswa ngokuphindwe kathathu kwinwebu ye-mesoscopic yomlambo ngamnye.Zonke iikhemikhali kunye nedatha yebhayoloji njengenxalenye yovavanyo lwe-mesoscopic lubonelelwe ngokukhutshwa kwedatha ehamba kunye (35).
Uphando lwe-ecological lwenziwa kwimijelo emincinci (wading) kwimimandla emihlanu emikhulu yase-United States, kwaye izibulali-zinambuzane zabekwa iliso ngexesha lesalathisi sangaphambili.Ngamafutshane, ngokusekelwe kusetyenziso lomhlaba wezolimo kunye needolophu (36-40), i-77 kwiindawo ze-100 zikhethwe kwindawo nganye (iindawo ze-444 zizonke).Ngexesha lentwasahlobo kunye nehlobo lonyaka omnye (2013-2017), iisampuli zamanzi ziqokelelwa kanye ngeveki kwingingqi nganye kwiiveki ezi-4 ukuya kwezi-12.Ixesha elichanekileyo lixhomekeke kwingingqi kunye nokuqina kophuhliso.Noko ke, izikhululo ezili-11 ezikummandla osemntla-mpuma ziphantse zibe kwindawo enamanzi.Akukho phuhliso, ngaphandle kokuba isampuli enye kuphela eqokelelweyo.Ekubeni amaxesha okubeka iliso kwizitshabalalisi kwizifundo zengingqi ahlukile, xa kuthelekiswa, kuphela ziisampuli ezine zokugqibela eziqokelelwe kwindawo nganye eziqwalaselwayo apha.Kucingelwa ukuba isampuli enye eqokelelwe kwindawo engaphuhliswanga ye-Northeast site (n = 11) inokumela ixesha le-sampling yeeveki ezi-4.Le ndlela ikhokelela kwinani elifanayo lokuqwalaselwa kwi-pesticides (ngaphandle kweendawo ze-11 kuMntla-mpuma) kunye nexesha elifanayo lokujonga;kukholelwa ukuba iiveki ezi-4 zinde ngokwaneleyo ukuba zisesichengeni sexesha elide kwi-biota, kodwa zifutshane ngokwaneleyo ukuba uluntu lwe-ecology alufuni.
Kwimeko yokuhamba okwaneleyo, isampuli yamanzi iqokelelwa ngendlela yesantya kunye nokunyuka kobubanzi obuqhubekayo (41).Xa ukuhamba kunganelanga ukusebenzisa le ndlela, unokuqokelela iisampulu ngokudityaniswa okunzulu kweesampuli okanye ukubamba ukusuka kwiziko lomxhuzulane wokuhamba.Sebenzisa i-syringe enkulu kunye ne-disc filter (0.7μm) ukuqokelela i-10 ml yesampuli ehluziweyo (42).Nge-DAI LC-MS/MS/MS/MS, iisampulu zamanzi zahlalutywa kwi-NWQL kwi-225 ye-pesticides kunye neemveliso zokuthotywa kwe-pesticide, kuquka i-fipronil kunye ne-7 yeemveliso zokunciphisa (dessulfinyl fipronil, fipronil) Sulfides, fipronil sulfone, deschlorofipronil, fipronil, fipronil, i-fipronil kunye ne-fipronil).).Amanqanaba aqhelekileyo okunika ingxelo kwizifundo zasendle ngala: fipronil, desmethylthio fluorobenzonitrile, fipronil sulfide, fipronil sulfone, kunye nedeschlorofipronil 0.004 μg/L;i-dessulfinyl fluorfenamide kunye ne-concentration ye-fipronil amide yi-0.009 μg/litre;Uxinzelelo lwe-fipronil sulfonate ngu-0.096 μg/litre.
Uluntu lwezilwanyana ezingenamqolo luthathwa iisampulu ekupheleni kophononongo lwendawo nganye (entwasahlobo/ehlotyeni), ngokuqhelekileyo ngexesha elinye nesiganeko sokugqibela sokuthatha iisampulu zesitshabalalisi.Emva kwexesha lokukhula kunye nokusetyenziswa kakhulu kwezibulali zinambuzane, ixesha lokuthatha iisampulu kufuneka lihambelane neemeko zokuhamba okuphantsi, kwaye kufuneka lihambelane nexesha apho uluntu lwe-invertebrate yomlambo luvuthwa kwaye ubukhulu becala kwinqanaba lobomi bombungu.Ukusebenzisa i-Surber sampler ene-500μm mesh okanye i-D-frame net, isampuli yoluntu ye-invertebrate yagqitywa kwi-437 kwi-444 sites.Indlela yesampulu ichazwe ngokweenkcukacha kwimathiriyeli eyongezelelweyo.Kwi-NWQL, zonke izilwanyana ezingenamqolo zidla ngokuchongwa kwaye zidweliswe kwinqanaba le-genus okanye leentlobo.Yonke idatha yeekhemikhali kunye ne-biological eqokelelwe kule ntsimi kwaye isetyenziswe kulo mbhalo wesandla inokufumaneka kwi-data ehambelanayo yokukhutshwa (35).
Kwimichiza emihlanu ye-fipronil esetyenziswe kuvavanyo lwe-mesoscopic, ukuxinwa kwee-larval invertebrates ezincitshiswe nge-20% okanye i-50% zibalwe ngokumalunga nolawulo (okt EC20 kunye ne-EC50).Idatha [x = ixesha-weighted fipronil concentration (jonga imathiriyeli eyongezelelweyo ngeenkcukacha), y = i-larval abundance okanye ezinye ii-metrics] zifakwe kwi-R (43) iphakheji eyandisiweyo kusetyenziswa indlela ye-logarithmic regression ye-parameter ezintathu" drc".Igophe lilungele zonke iintlobo (imibungu) ngobuninzi obaneleyo kwaye idibana nezinye iimetrikhi zomdla (umzekelo, ubutyebi betaxa, ubuninzi be-mayfly buphelele, kunye nobuninzi obupheleleyo) ukuqonda ngakumbi isiphumo soluntu.I-coefficient ye-Nash-Sutcliff (45) isetyenziselwa ukuvavanya ukulinganisa kwemodeli, apho imodeli engafanelekanga inokufumana amaxabiso angenasiphelo angalunganga, kwaye ixabiso lokulinganisa ngokugqibeleleyo ngu-1.
Ukuphonononga imiphumo ye-fipronil compounds ekuveleni kwezinambuzane kuvavanyo, idatha yavavanywa ngeendlela ezimbini.Okokuqala, ngokuthabatha inkangeleko engumndilili wokuqukuqela kwe-meso kwinkangeleko yonyango ngalunye lokuqukuqela i-meso, ukwenzeka okongezelekayo kwemihla ngemihla kwezinambuzane ukusuka kwi-meso nganye yokuqukuqela (inani lilonke labo bonke abantu) laye lahlengahlengiswa kulawulo.Cwangcisa la maxabiso ngokuchasene nexesha lokuqonda ukutenxa komlamli wolwelo lonyango ukusuka kumlamli wolwelo lolawulo kuvavanyo lweentsuku ezingama-30.Okwesibini, bala ipesenti yokwenzeka kwe-mesophyll nganye, echazwa njengomlinganiselo wenani elipheleleyo le-mesophyll kwi-flow enikeziweyo ukuya kumyinge wenani leembungu kunye nabantu abadala kwiqela lolawulo, kwaye ifanelekile kwi-logarithmic regression yeparameter ezintathu. .Zonke izinambuzane ezihlumayo eziqokelelweyo zazisuka kwiintsapho ezincinci ezimbini zentsapho yaseChironomidae, ngoko ke uhlalutyo oludibeneyo lwenziwa.
Utshintsho kulwakhiwo loluntu, olufana nokulahleka kwerhafu, lunokuthi ekugqibeleni luxhomekeke kwiziphumo ezithe ngqo nezingathanga ngqo zezinto eziyityhefu, kwaye zinokukhokelela kutshintsho kumsebenzi woluntu (umzekelo, itrophic cascade).Ukuvavanya i-trophic cascade, inethiwekhi ye-causal elula yavavanywa ngokusebenzisa indlela yokuhlalutya indlela (i-R package "piecewiseSEM") (46).Kwimifuniselo ye-mesoscopic, kucingelwa ukuba i-fipronil, i-desulfinyl, i-sulfide kunye ne-sulfone (engavavanywanga i-amide) emanzini ukunciphisa i-biomass ye-scraper, ikhokelela ngokungathanga ngqo ekwandeni kwe-biomass ye-chlorophyll a (47).I-concentration concentration yi-predictor variable, kunye ne-scraper kunye ne-chlorophyll i-biomass yimiba yokuphendula.I-Fisher's C statistic isetyenziselwa ukuvavanya ukufaneleka kwemodeli, ukuze ixabiso le-P <0.05 libonise imodeli efanelekileyo efanelekileyo (46).
Ukuze kuphuhliswe i-ejenti yokukhusela i-eco-community threshold, i-compound nganye ifumene i-95% yeentlobo ezichaphazelekayo (HC5) ukusabalalisa uvakalelo olungapheliyo (SSD) kunye nokukhuselwa koxinzelelo lwengozi.Iiseti ezintathu zedatha ye-SSD zenziwe: (i) kuphela iseti yedatha ye-meso, (ii) iseti yedatha equlethe yonke idatha ye-meso kunye nedatha eqokelelwe kwi-EPA ECOTOX umbuzo wesiseko sedatha (https://cfpub.epa.gov/ecotox) /, ifikelelwe NgoMatshi 14, 2019), ubude bexesha lokufunda ziintsuku ezi-4 okanye ngaphezulu, kwaye (iii) isethi yedatha equlethe yonke idatha ye-mesoscopic kunye nedatha ye-ECOTOX, apho idatha ye-ECOTOX (i-acute exposure) yahlulwe ngokukrakra ukuya kumlinganiselo we-D. 19.39) ukucacisa umahluko kwixesha lokuvezwa kunye nokulinganisa ixabiso elingapheliyo le-EC50 (12).Injongo yethu yokuvelisa iimodeli ezininzi ze-SSD kuku (i) ukuphuhlisa amaxabiso e-HC5 ukuze kuthelekiswe nedatha yasendle (kuphela ii-SSD zemidiya), kunye (ii) nokuvavanya ukuba idatha yemidiya yamkelwe ngokubanzi kunee-arhente ezilawulayo ukuba zibandakanywe kwi-aquaculture. Ukomelela kweempawu zobomi kunye nokusekwa okusemgangathweni kwemithombo yedatha, kwaye ke ngoko ukukwazi ukusebenzisa izifundo ze-mesoscopic kwinkqubo yohlengahlengiso.
I-SSD yaphuhliswa kwiseti nganye yedatha kusetyenziswa iphakheji ye-R "ssdtools" (48).Sebenzisa i-bootstrap (n = 10,000) ukuqikelela umyinge we-HC5 kunye nekhefu lokuzithemba (CI) ukusuka kwi-SSD.Amashumi amane anesithoba eempendulo zetaxa (zonke iirhafu ezichongiweyo njengohlobo okanye iintlobo) eziphuhliswe ngolu phando zidityaniswe neempendulo zetaxa ezingama-32 ezihlanganiswe kwizifundo ezintandathu ezipapashiweyo kwisiseko sedatha se-ECTOX, kwi-81 iyonke impendulo yeTaxon ingasetyenziselwa uphuhliso lwe-SSD. .Ekubeni akukho datha efunyenwe kwi-database ye-ECOTOX ye-amides, akukho SSD yaphuhliswa kwi-amides kwaye enye kuphela impendulo ye-EC50 ifunyenwe kwisifundo samanje.Nangona ixabiso le-EC50 leqela elilodwa le-sulfide lifunyenwe kwi-database ye-ECOTOX, umfundi ophumeleleyo ngoku unemilinganiselo ye-12 EC50.Ngoko ke, ii-SSD zamaqela e-sulfinyl ziye zaphuhliswa.
Amaxabiso athile eHC5 eekhompawundi zefipronil afunyenwe kwiseti yedatha ye-SSD yeMesocosmos kuphela adityaniswe nedatha yasendle ukuvavanya ukuvezwa kunye netyhefu enokubakho yeekhompawundi zefipronil kwimijelo engama-444 evela kwimimandla emihlanu eUnited States.Kwifestile yokugqibela yeesampulu ze-4-iveki, i-concentration nganye ye-fipronil compounds efunyenweyo (i-concentrations engabonwanga yi-zero) yahlulwe yi-HC5 yayo, kwaye umlinganiselo we-compound wesampulu nganye ushwankathelwa ukufumana Iyunithi ye-toxicity epheleleyo ye-fipronil (ΣTUFipronils), apho ΣTUFipronils> 1 ithetha ubutyhefu.
Ngokuthelekisa i-50% yengozi yoxinzelelo lwe-50% yeentlobo ezichaphazelekayo (HC50) kunye nexabiso le-EC50 lobutyebi be-taxa ephuma kuvavanyo lwe-membrane ephakathi, i-SSD efunyenwe kwidatha ye-membrane ephakathi iye yavavanywa ukubonisa ubuntununtunu boluntu olubanzi lwe-ecological kwi-fipronil. isidanga..Ngolu thelekiso, ukuhambelana phakathi kwendlela ye-SSD (kubandakanywa kuphela ezo taxa kunye nobudlelwane be-dose-response) kunye nendlela ye-EC50 (kubandakanywa nayo yonke i-taxa ekhethekileyo ebonwe kwindawo ephakathi) usebenzisa indlela ye-EC50 yokulinganisa ubutyebi be-taxa inokuvavanywa ngesondo.Ubudlelwane bempendulo yethamo.
Uhlobo lwengozi ye-pesticides (i-SPEARpesticides) isalathisi yabalwa ukuphanda ubudlelwane phakathi kwemeko yempilo yoluntu lwe-invertebrate kunye ne-ΣTUFipronil kwi-437 invertebrate-collecting streams.Imetric ye-SPEARpesticides iguqula ukubunjwa kwezilwanyana ezingenamqolo zibe yintaphane metric yebhayoloji yetaxonomy eneempawu zefiziyoloji kunye ne-ikholoji, ngaloo ndlela inika ubuntununtunu kwizitshabalalisi.Isalathisi se-SPEARpesticides asikhathaleli kwi-covariates yendalo (49, 50), nangona ukusebenza kwayo kuya kuchatshazelwa kukuwohloka okukhulu kwendawo yokuhlala (51).Ubuninzi bedatha eqokelelwe kwindawo yetaxon nganye ilungelelaniswa nexabiso eliphambili lerhafu elinxulumene nesoftware ye-ASTERICS yokuvavanya umgangatho wendalo yomlambo (https://gewaeser-bewertung-berechnung.de/index.php/home html).Emva koko ngenisa idatha kwi-Indicate (http://systemecology.eu/indicate/) software (version 18.05).Kule software, i-database ye-European trait kunye ne-database enovakalelo lwe-physiological kwi-pesticides isetyenziselwa ukuguqula idatha yesayithi nganye kwisalathisi se-SPEARpesticides.Uphononongo ngalunye kwezintlanu zengingqi lusebenzise i-General Additive Model (GAM) ["mgcv" ipakethe kwi-R (52)) ukuphonononga ubudlelwane phakathi kwe-SPEARpesticides metric kunye ne-ΣTUFipronils [log10 (X + 1) conversion] Associated.Ngolwazi oluthe vetshe nge-SPEARpesticides metrics kunye nohlalutyo lwedatha, nceda ubone i-Supplementary Materials.
Isalathiso somgangatho wamanzi siyangqinelana ekuhambeni kwe-mesoscopic nganye kunye nalo lonke ixesha lovavanyo lwe-mesoscopic.Ubushushu obuqhelekileyo, i-pH kunye ne-conductivity yayiyi-13.1 ° C (± 0.27 ° C), 7.8 (± 0.12) kunye ne-54.1 (± 2.1) μS / cm (35), ngokulandelanayo.Umlinganiselo wekhabhoni enyityilisiweyo enyibilikisiweyo kumanzi omlambo acocekileyo yi-3.1 mg/L.Kwimbono ye-meso yomlambo apho irekhoda ye-MiniDOT ibekwe khona, i-oksijini enyibilikisiweyo isondele kwi-saturation (i-avareji> 8.0 mg/L), ebonisa ukuba umlambo ujikelezwe ngokupheleleyo.
Ukulawulwa komgangatho kunye nedatha yokuqinisekisa umgangatho kwi-fipronil inikezelwa ekukhutshweni kwedatha ehamba kunye (35).Ngamafutshane, amazinga okubuyisela i-labhoratri ye-matrix spikes kunye neesampuli ze-mesoscopic zikholisa ukuba phakathi koluhlu olwamkelekileyo (ukufumana kwakhona kwe-70% ukuya kwi-130%), imigangatho ye-IDL iqinisekisa indlela yobuninzi, kunye ne-laboratory kunye nezixhobo ezingenanto zihlala zicocekile. oku kuxutyushwa ngokubanzi kumbandela owongezelelweyo..
Ngenxa yoyilo lwenkqubo, i-concentration elinganisiweyo ye-fipronil ngokuqhelekileyo iphantsi kwexabiso elijoliswe kuyo (Umfanekiso we-S2) (kuba kuthatha i-4 kwiintsuku ze-10 ukufikelela kwindawo ezinzileyo phantsi kweemeko ezifanelekileyo) (30).Xa kuthelekiswa nezinye iikhompawundi ze-fipronil, i-concentration ye-desulfinyl kunye ne-amide itshintsha kancinci ngokuhamba kwexesha, kwaye ukuhluka koxinzelelo ngaphakathi kwonyango kuncinci kunomahluko phakathi konyango ngaphandle konyango oluphantsi lwe-sulfone kunye ne-sulfide.Umyinge wexesha lokulinganisa umlinganiselo woxinaniso olulinganisiweyo kwiqela ngalinye lonyango lulandelayo: I-Fipronil, i-IDL ukuya kwi-9.07μg / L;I-Desulfinyl, i-IDL ukuya kwi-2.15μg / L;I-Amide, i-IDL ukuya kwi-4.17μg / L;Sulfidi, IDL Ukuya kwi-0.57μg/litre;kunye ne-sulfone, i-IDL yi-1.13μg/litre (35).Kweminye imijelo, iikhompawundi ze-fipronil ezingajoliswanga zichongiwe, oko kukuthi, iikhompawundi ezingazange zifakwe kunyango oluthile, kodwa zaziwa njengemveliso yokuthotywa kwekhompawundi yonyango.I-membrane ye-mesoscopic ephathwa nge-fipronil yekhompawundi yomzali inelona nani liphezulu leemveliso zokuthotywa kwe-non-target efunyenweyo (xa zingasetyenziswanga njenge-compound processing, ziyi-sulfinyl, i-amide, i-sulfide kunye ne-sulfone);ezi zinokuba ngenxa yenkqubo yokuvelisa Ukungcola okudibeneyo kunye / okanye iinkqubo zokunciphisa okwenzeka ngexesha lokugcinwa kwesisombululo sesitokhwe kunye (okanye) kuvavanyo lwe-mesoscopic kunokuba umphumo wokungcola.Akukho mkhwa wokuxinana kokuthotywa kwabonwa kunyango lwe-fipronil.Iikhompawundi zokuthotywa kwe-target engezona-thagethi zibonwa ngokuqhelekileyo emzimbeni ngoxinaniso lonyango oluphezulu, kodwa ugxininiso lungaphantsi koxinzelelo lwezi zixhobo ezingajoliswanga (jonga icandelo elilandelayo lokugxila).Ke ngoko, ekubeni iikhompawundi zokuthotywa okungajoliswanga kuzo zihlala zingabonwa kolona nyango lusezantsi lwefipronil, kwaye ngenxa yokuba ugxininiso olufunyenweyo lusezantsi kunoxinzelelo lwesiphumo kunyango oluphezulu, kuqukunjelwa ukuba ezi khompawundi zingajoliswanga zinempembelelo encinci kuhlalutyo.
Kwiimvavanyo zemidiya, i-benthic macroinvertebrates yayinovelwano kwi-fipronil, i-desulfinyl, i-sulfone, kunye ne-sulfide [Itheyibhile S1;idatha yobuninzi boqobo inikezelwe kwinguqulelo yedatha ehamba kunye (35)].IFipronil amide yeyempukane iRhithrogena sp.Ityhefu (ebulalayo), i-EC50 yayo yi-2.05μg/L [±10.8(SE)].I-dose-response curves ye-15 unique taxa yenziwa.Ezi taxa zibonise ukufa phakathi koluhlu loxinaniso oluvavanyiweyo (Itheyibhile S1), kunye ne-tax edibeneyo ekujoliswe kuyo (njengeempukane) (Umfanekiso S3) kunye ne-taxa etyebileyo (Umfanekiso 1) Igophe lempendulo yethamo yenziwe.I-concentration (EC50) ye-fipronil, i-desulfinyl, i-sulfone kunye ne-sulfide kwi-taxa ekhethekileyo ye-taxa enzima kakhulu ukusuka kwi-0.005-0.364, 0.002-0.252, 0.002-0.061 kunye ne-0.005-0.043μg / L, ngokulandelanayo.Rhithrogena sp.Kwaye uSweltsa sp.;Umzobo we-S4) ungaphantsi kune-taxa enyamezelekileyo (efana ne-Micropsectra / Tanytarsus kunye ne-Lepidostoma sp.) (Itheyibhile S1).Ngokomndilili we-EC50 wekhompawundi nganye kwiThebhile S1, i-sulfones kunye ne-sulfides zezona zixhobo zisebenzayo, ngelixa ii-invertebrates ngokuqhelekileyo ziyizona mvakalelo zincinci kwi-desulfinyl (ngaphandle kwe-amides).Iimetrics zesimo se-ikholoji ngokubanzi, ezifana nobutyebi betaxa, ubuninzi obupheleleyo, i-pentaploid iyonke kunye ne-stone fly iyonke, kubandakanywa i-taxa kunye nobuninzi be-taxa ethile, ezi zinqabile kakhulu kwi-meso kwaye azinakubalwa Zoba igophe lokuphendula idosi eyahlukileyo.Ke ngoko, ezi zalathi zendalo zibandakanya iimpendulo zerhafu ezingafakwanga kwi-SSD.
Ubutyebi be-Taxa (umbungu) kunye nomsebenzi owenziwe ngamanqanaba amathathu e-(A) i-fipronil, (B) i-desulfinyl, (C) i-sulfone, kunye (i-D) ne-concentration ye-sulfide.Inqaku ngalinye ledatha limele imibungu evela kumlambo omnye ekupheleni kovavanyo lwe-meso lweentsuku ezingama-30.Ubutyebi berhafu lubalo lwerhafu eyodwa kumsinga ngamnye.Ixabiso loxinaniso yi-avareji yobunzima bexesha lokuxinana okuphawulweyo kumsinga ngamnye olinganiswe ekupheleni komfuniselo weentsuku ezingama-30.I-Fipronil amide (engaboniswanga) ayinabudlelwane kunye ne-taxa ecebileyo.Nceda uqaphele ukuba i-x-axis ikumlinganiselo welogarithmic.I-EC20 kunye ne-EC50 ene-SE zichazwe kwiThebhile S1.
Kweyona ndawo iphezulu yoxinaniso kuzo zontlanu iikhompawundi zefipronil, izinga lokuvela kwe-Uetridae lehlile.Ipesenti yokuhluma (EC50) ye-sulfide, i-sulfone, i-fipronil, i-amide kunye ne-desulfinyl yabonwa ukuba iyancipha nge-50% kwi-concentrations ye-0.03, 0.06, 0.11, 0.78 kunye ne-0.97μg / L ngokulandelanayo (Umfanekiso 2 kunye noMfanekiso S5).Kwiimvavanyo ezininzi zeentsuku ze-30, zonke iindlela zonyango ze-fipronil, i-desulfinyl, i-sulfone kunye ne-sulfide zalibaziseka, ngaphandle konyango oluthile oluphantsi (Umfanekiso we-2), kwaye ukubonakala kwabo kwakunqatshelwe.Kunyango lwe-amide, ukungcola okuqokelelweyo ngexesha lovavanyo lonke kwakuphezulu kunolawulo, kunye noxinzelelo lwe-0.286μg / litre.Uxinzelelo oluphezulu (i-4.164μg / ilitha) ngexesha lovavanyo lonke luthintele ukungcola, kwaye isantya sokungcola kwonyango oluphakathi lwalufana nelo qela lokulawula.(umzobo 2).
Ukuvela okukhulayo yi-avareji ye-avareji yemihla ngemihla yokuvela konyango ngalunye lokuthabatha (A) i-fipronil, (B) i-desulfinyl, (C) i-sulfone, (D) i-sulfide kunye (i-E) ne-amide kumlambo wokulawula Umndilili wemihla ngemihla wokuvela kwenwebu.Ngaphandle kolawulo (n = 6), n = 1. Ixabiso lokugxininiswa liyi-avareji yokulinganisa ixesha lokugxininiswa okubonwayo ekuhambeni ngalunye.
I-curve ye-dose-response curve ibonisa ukuba, ukongeza kwilahleko ye-taxonomic, utshintsho lwesakhiwo kwinqanaba loluntu.Ngokukodwa, ngaphakathi koluhlu loxinaniso lovavanyo, ubuninzi be-May (Umfanekiso S3) kunye nobuninzi be-taxa (Umfanekiso 1) ubonise ubudlelwane obubalulekileyo bokuphendula umthamo kunye ne-fipronil, i-desulfinyl, i-sulfone, kunye ne-sulfide.Ke ngoko, siye saphonononga ukuba olu tshintsho lwesakhiwo lukhokelela njani kutshintsho ekusebenzeni koluntu ngokuvavanya i-cascade yesondlo.Ukubonakaliswa kwama-invertebrates asemanzini kwi-fipronil, i-desulfinyl, i-sulfide kunye ne-sulfone inefuthe elibi ngqo kwi-biomass ye-scraper (Umfanekiso 3).Ukuze kulawulwe impembelelo embi yefipronil kwi-biomass ye-scraper, i-scraper nayo yachaphazela kakubi i-chlorophyll i-biomass (Umfanekiso 3).Isiphumo sala ma-coefficients eendlela ezimbi kukunyuka okunetha kwi-chlorophyll a njengoko ukuxinwa kwe-fipronil kunye ne-degradants kuyanda.Le mifuziselo yeendlela ezilungelelanisiweyo zibonisa ukuba ukonakaliswa okwandisiweyo kwe-fipronil okanye i-fipronil kukhokelela ekwandeni komlinganiselo we-chlorophyll a (Umfanekiso 3).Kucingelwa kwangaphambili ukuba isiphumo esithe ngqo phakathi kwe-fipronil okanye i-degradation concentration kunye ne-chlorophyll i-biomass yi-zero, kuba iikhompawundi ze-fipronil zizibulali-zinambuzane kwaye zinetyhefu ephantsi ngokuthe ngqo kwi-algae (umzekelo, i-EPA acute non-vascular plant concentration yi-100μg / L. i-fipronil, iqela le-disulfoxide, i-sulfone kunye ne-sulfide https://epa.gov/pesticide-science-and-assessing-pesticide-risk/aquatic-life-benchmarks-and-ecological-risk), Zonke iziphumo (imifuziselo esebenzayo) zixhasa oku; ingcamango.
I-Fipronil inokunciphisa kakhulu i-biomass (impembelelo ethe ngqo) yokutyisa (iqela le-scraper yimibungu), kodwa ayinayo impembelelo ethe ngqo kwi-biomass ye-chlorophyll a.Nangona kunjalo, isiphumo esinamandla esingathanga ngqo se-fipronil kukwandisa i-biomass ye-chlorophyll a ukuphendula amadlelo amancinci.Utolo lubonisa i-coefficient yendlela esemgangathweni, kwaye uphawu lokuthabatha (-) lubonisa isalathiso sonxulumano.* Ubonisa inqanaba lokubaluleka.
Ii-SSD ezintathu (umaleko ophakathi kuphela, umaleko ophakathi kunye nedatha ye-ECOTOX, kunye nomgangatho ophakathi kunye nedatha ye-ECOTOX elungiswe umahluko kubude bexesha lokuvezwa) zivelise amaxabiso ahlukeneyo e-HC5 (Itheyibhile S3), kodwa iziphumo bezingaphakathi kuluhlu lwe-SE.Kulo lonke olu phononongo, siya kugxila kwi-SSD yedatha enendalo ye-meso kuphela kunye nexabiso le-HC5 elinxulumeneyo.Ukufumana inkcazo epheleleyo yolu vavanyo lwe-SSD zintathu, nceda ubhekisele kwizinto ezongezelelweyo (Iitheyibhile S2 ukuya kwi-S5 kunye neFigure S6 kunye ne-S7).Olona nikezelo lwedatha lulona (olona lwazi lusezantsi lwe-Akaike lwamanqaku asezantsi) lwezikhompawundi ezine zefipronil (Umfanekiso 4) osetyenziswa kuphela kwimephu ye-SSD ye-meso-solid yilog-gumbel yefipronil kunye nesulfone, kunye ne-weibull yesulfide kunye ne-desulfurized γ ( Uluhlu S3).Amaxabiso eHC5 afunyenwe kwikhompawundi nganye axelwe kuMfanekiso 4 wendalo yonke ye-meso kuphela, kwaye kwiThebhile S3 amaxabiso eHC5 kuzo zontathu iiseti zedatha ye-SSD zixeliwe.Amanani eHC50 yefipronil, sulfide, sulfone kunye namaqela e-desulfinyl [22.1±8.78 ng/L (95% CI, 11.4 ukuya ku-46.2), 16.9±3.38 ng/L (95% CI, 11.2 ukuya ku-28.0±) 2.66 ng/L (95% CI, 5.44 ukuya ku-15.8) kunye ne-83.4±32.9 ng/L (95% CI, 36.4 ukuya ku-163)] Ezi zixhobo ziphantsi kakhulu kunobutyebi be-EC50 taxa (inani lilonke le-taxa eyodwa) (Itheyibhile S1 ;
Kwimvavanyo ye-meso-scale, xa ibonakaliswe (A) i-fipronil, (B) i-dessulfinyl fipronil, (C) i-fipronil sulfone, (D) i-fipronil sulfide yeentsuku ze-30, uhlobo lobuntu buchazwa Lixabiso le-EC50 le-taxon.Umgca ohlaza okwesibhakabhaka umele i-95% CI.Umgca oxwesileyo oxwesileyo umele iHC5.Ixabiso leHC5 (ng / L) yekhompawundi nganye ngolu hlobo lulandelayo: Fipronil, 4.56 ng / L (95% CI, 2.59 ukuya ku-10.2);Sulfidi, 3.52 ng / L (1.36 ukuya ku-9.20);Sulfone, 2.86 ng/ Litre (1.93 ukuba 5.29);kunye ne-sulfinyl, 3.55 ng / ilitha (0.35 ukuya ku-28.4).Nceda uqaphele ukuba i-x-axis ikumlinganiselo welogarithmic.
Kwizifundo ezihlanu zengingqi, i-Fipronil (abazali) yafunyanwa kwi-22% yeendawo ze-444 zesampula (Itheyibhile 1).I-frequency yokufunyanwa kwe-florfenib, i-sulfone kunye ne-amide iyafana (i-18% ukuya kwi-22% yesampuli), i-frequency yokubona i-sulfide kunye ne-desulfinyl iphantsi (i-11% ukuya kwi-13%), ngelixa iimveliso eziseleyo zokuthotywa ziphezulu kakhulu.Bambalwa (1% okanye ngaphantsi) okanye abazange babhaqwe (Itheyibhile 1)..I-Fipronil ifunyenwe rhoqo kumzantsi-mpuma (i-52% yeziza) kwaye incinci rhoqo kumntla-ntshona (i-9% yeziza), ebonisa ukuguquguquka kokusetyenziswa kwe-benzopyrazole kunye nokuba sesichengeni somlambo onokwenzeka kwilizwe lonke.I-Degradants idla ngokubonisa iipateni zengingqi ezifanayo, kunye neyona ndawo iphezulu yokuchongwa kumzantsi-mpuma kunye neyona isezantsi kumntla-ntshona okanye unxweme lwaseCalifornia.I-concentration elinganisiweyo ye-fipronil yayiphezulu, ilandelwa yi-fipronil edibeneyo yomzali (ipesenti ze-90% ze-10.8 kunye ne-6.3 ng / L, ngokulandelanayo) (Itheyibhile 1) (35).I-concentration ephezulu ye-fipronil (61.4 ng / L), i-disulfinyl (10.6 ng / L) kunye ne-sulfide (8.0 ng / L) inqunywe kumzantsi-mpuma (kwiiveki ezine zokugqibela zesampuli).Olona xinzelelo luphezulu lwesulfone lwamiselwa entshona.(15.7 ng / L), i-amide (42.7 ng / L), i-dessulfinyl flupirnamide (14 ng / L) kunye ne-fipronil sulfonate (8.1 ng / L) (35).I-Flofenide sulfone yayikuphela kwekhompawundi eyayiqatshelwe ukuba idlule i-HC5 (Itheyibhile 1).Umyinge we-ΣTUFipronils phakathi kwemimandla eyahlukeneyo iyahluka kakhulu (Itheyibhile 1).Umyinge wesizwe ΣTUFipronils ngu-0.62 (zonke iindawo, zonke iingingqi), kunye neendawo ze-71 (16%) zine-ΣTUFipronils> 1, ebonisa ukuba ingaba yingozi kwi-benthic macroinvertebrates.Kwimimandla emine kwemihlanu ephononongwayo (ngaphandle kweMidwest), kukho ubudlelwane obubalulekileyo phakathi kwe-SPEARpesticides kunye ne-ΣTUFipronil, kunye ne-R2 ehlengahlengisiweyo ukusuka kwi-0.07 kunxweme lwaseCalifornia ukuya kwi-0.34 kumzantsi-mpuma (Umfanekiso 5).
*Iikhompawundi ezisetyenziswa kwimifuniselo ye-mesoscopic.† ΣTUFipronils, i-median ye-sum of toxin units [ibonwe kwintsimi yoxinzelelo lwe-fipronil compounds ezine / i-hazard concentration ye-compound nganye ukusuka kwi-percentile yesihlanu yeentlobo ze-SSD-intsholongwane (Umfanekiso 4)] Kwiisampuli zeveki ze-fipronil, i-4 yokugqibela iiveki zeesampulu zezitshabalalisi eziqokelelwe kwindawo nganye zibaliwe.• Inani leendawo apho kulinganiswa khona izibulali-zinambuzane.§Ipesenti ezingama-90 isekwe kugxininiso olukhulu olujongwe kwisiza kwiiveki ezi-4 zokugqibela zokuthatha iisampulu yesibulali-zinambuzane.ngepesenti yeesampuli ezivavanyiweyo.¶ Sebenzisa i-95% CI yexabiso leHC5 (Umfanekiso 4 kunye neThebhile S3, i-meso kuphela) ukubala i-CI.I-Dechloroflupinib iye yahlalutywa kuyo yonke imimandla kwaye ayizange ifunyanwe.ND, ayifunyaniswanga.
Iyunithi yetyhefu ye-Fipronil ngumlinganiselo we-fipronil yoxinaniso eyahlulahlulwe ngexabiso le-HC5 yekhompawundi ethile, egqitywe yi-SSD efunyenwe kumfuniselo wemidiya (jonga uMfanekiso 4).Umgca omnyama, imodeli yokongeza ngokubanzi (GAM).Umgca obomvu obomvu une-CI ye-95% ye-GAM.ΣTUFipronils iguqulelwa kwilog10 (ΣTUFipronils+1).
Imiphumo emibi ye-fipronil kwiintlobo zezilwanyana zasemanzini ezingajoliswanga zibhalwe kakuhle (15, 21, 24, 25, 32, 33), kodwa olu luphononongo lokuqala apho lunovakalelo kwindawo yebhubhoratri elawulwayo.Uluntu lwerhafu luye lwachanabeka kwiikhompawundi zefipronil, kwaye iziphumo zaye zachazwa ngokomlinganiselo welizwekazi.Iziphumo zovavanyo lwe-mesocosmic lweentsuku ezingama-30 zinokuvelisa amaqela ezinambuzane zasemanzini ezili-15 (Itheyibhile S1) kunye nokugxininiswa okungaxelwanga kuncwadi, phakathi kwazo izinambuzane zasemanzini kwi-database ye-toxicity azimele (53, 54).I-Taxa-specific dose-responce curves (efana ne-EC50) ibonakaliswe kutshintsho lwezinga loluntu (njengobutyebi be-taxa kwaye inokubhabha ilahleko eninzi) kunye neenguqu zokusebenza (ezifana ne-cascade yesondlo kunye nokutshintsha kwenkangeleko).Umphumo wendalo yonke ye-mesoscopic wagqithiselwa kwintsimi.Kwiindawo ezine kwezintlanu zophando e-United States, i-fipronil yokulinganisa intsimi yayihambelana nokuhla kwe-ecosystem yasemanzini emanzini ahambayo.
Ixabiso le-HC5 le-95% yeentlobo kuvavanyo lwe-membrane oluphakathi lunempembelelo yokukhusela, ebonisa ukuba uluntu jikelele lwezilwanyana zasemanzini ezingenamqolo zivakalelwa ngakumbi kwiikhompawundi ze-fipronil kunokuba zaziqondwa ngaphambili.Ixabiso leHC5 elifunyenweyo (florfenib, 4.56 ng/litre; desulfoxirane, 3.55 ng/litre; sulfone, 2.86 ng/litre; sulfide, 3.52 ng/litre) amaxesha amaninzi (florfenib) ukuya kathathu Ngaphezu komyalelo wobukhulu (desulfinyl) ) ngaphantsi kwe-EPA engapheliyo ye-invertebrate benchmark yangoku [fipronil, 11 ng / litre;desulfinyl, 10,310 ng/litre;sulfone, 37 ng/litre;kunye ne-sulfide, ye-110 ng/litre (8)].Iimvavanyo ze-Mesoscopic zichonge amaqela amaninzi anomdla kwi-fipronil endaweni yalawo aboniswe yi-EPA engapheliyo ye-invertebrate benchmark (amaqela e-4 avakalelwa kakhulu kwi-fipronil, i-13 pairs of desulfinyl, i-11 pairs of sulfone kunye ne-13 pairs) i-sulfide sensitivity) (Umfanekiso 4 kunye itafile) S1).Oku kubonisa ukuba iibenchmarks azikwazi ukukhusela iindidi ezininzi ezibonwa kumbindi wehlabathi, ezixhaphake kakhulu kwi-ecosystems yasemanzini.Umahluko phakathi kweziphumo zethu kunye nebenchmark yangoku ibangelwa ikakhulu kukungabikho kwedatha ye-fipronil toxicity test esebenzayo kuluhlu lwe-aquatic insect taxa, ngakumbi xa ixesha lokuvezwa lidlula iintsuku ezi-4 kwaye i-fipronil iyancipha.Ngethuba leentsuku ze-30 zovavanyo lwe-mesocosmic, ezininzi izinambuzane kwi-invertebrate community zazinovelwano ngakumbi kwi-fipronil kune-organism yovavanyo oluqhelekileyo i-Aztec (crustacean), nasemva kokulungisa i-Aztec I-EC50 ye-Teike yenza kube yinto efanayo emva kokuguqulwa kwenguqu.(Ngokuqhelekileyo iiyure ze-96) kwixesha elingapheliyo lokuvezwa (Umfanekiso S7).Imvumelwano engcono yafikelelwa phakathi kovavanyo lwe-membrane oluphakathi kunye nophononongo oluxelwe kwi-ECOTOX kusetyenziswa i-standard test organism Chironomus dilutus (inambuzane).Ayimangalisi into yokuba izinambuzane zasemanzini zinovelwano ngokukhethekileyo kwizibulali-zinambuzane.Ngaphandle kokulungelelanisa ixesha lokuvezwa, umfuniselo we-meso-scale kunye neenkcukacha ezibanzi ze-database ye-ECOTOX ibonise ukuba i-taxa eninzi ibonwe ukuba inovakalelo kwiikhompawundi ze-fipronil kune-Clostridium ehlanjululweyo (Figure S6).Nangona kunjalo, ngokulungelelanisa ixesha lokuvezwa, i-Dilution Clostridium yinto ebaluleke kakhulu kwi-fipronil (umzali) kunye ne-sulfide, nangona ingabonakali kwi-sulfone (Figure S7).Ezi ziphumo zibonisa ukubaluleka kokuquka iintlobo ezininzi zezinto eziphilayo zasemanzini (kubandakanywa nezinambuzane ezininzi) ukuvelisa imiyinge yokwenene yezibulali-zinambuzane ezinokukhusela izinto eziphilayo zasemanzini.
Indlela ye-SSD inokukhusela i-taxa enqabileyo okanye engabonakaliyo i-EC50 yayo ayinakuqinisekiswa, njengeCinygmula sp., Isoperla fulva kunye neBrachycentrus americanus.Amaxabiso e-EC50 obuninzi be-taxa kwaye inokubhabha ngobuninzi obubonisa utshintsho ekubunjweni koluntu luyahambelana namaxabiso eHC50 ye-SSD ye-fipronil, i-sulfone kunye ne-sulfide.Iprothokholi ixhasa le ngcamango ilandelayo: Indlela ye-SSD esetyenziselwa ukufumana i-thresholds inokukhusela uluntu lonke, kubandakanywa nerhafu enqabileyo okanye engabonakaliyo kuluntu.Umda wezinto eziphila emanzini ezimiselwe kwii-SSD ezisekelwe kwirhafu embalwa kuphela okanye irhafu engabalulekanga inokungonelanga kakhulu ukukhusela indalo yasemanzini.Le yimeko ye-desulfinyl (Umfanekiso we-S6B).Ngenxa yokungabikho kwedatha kwi-database ye-ECOTOX, i-EPA engapheliyo i-invertebrate concentration ye-invertebrate yi-10,310 ng / L, eyimiyalelo emine yobukhulu obuphezulu kune-3.55 ng / L ye-HC5.Iziphumo zeeseti ezahlukeneyo zeempendulo zetaxon eziveliswe kwimifuniselo ye-mesoscopic.Ukunqongophala kwedatha yetyhefu kuyingxaki ngokukodwa kwiikhompawundi ezinokonakala (Figure S6), enokuthi ichaze ukuba kutheni i-benchmarks yebhayoloji ekhoyo emanzini ye-sulfone kunye ne-sulfide imalunga ne-15 ukuya kwamaxesha angama-30 angaphantsi kwexabiso le-SSD HC5 esekelwe kwi-Universe yaseChina.Inzuzo yendlela ye-membrane ephakathi kukuba amaxabiso amaninzi e-EC50 anokuqinisekiswa kumfuniselo omnye, owaneleyo ukwenza i-SSD epheleleyo (umzekelo, i-desulfinyl; i-Figure 4B kunye neFigure S6B kunye ne-S7B), kwaye ibe nefuthe elibalulekileyo. kwirhafu yendalo ye-ikhosistim ekhuselweyo Iimpendulo ezininzi.
Uvavanyo lwe-Mesoscopic lubonisa ukuba i-fipronil kunye neemveliso zayo zokuthotywa zinokuba neziphumo ezicacileyo ezingabonakaliyo kunye nezingathanga ngqo kumsebenzi woluntu.Kuvavanyo lwe-mesoscopic, zontlanu iikhompawundi zefipronil zibonakale zichaphazela ukuvela kwezinambuzane.Iziphumo zokuthelekisa phakathi kweyona nto iphakamileyo kunye neyona nto iphantsi (ukuthintela kunye nokuvuselela ukuvela komntu okanye utshintsho kwixesha lokuvela) kuhambelana neziphumo ezichazwe ngaphambili ze-meso experiments usebenzisa i-insecticide bifenthrin (29).Ukuvela kwabantu abadala kunika imisebenzi ebalulekileyo ye-ecological kwaye inokuguqulwa ngezinto ezingcolileyo ezifana ne-fipronil (55, 56).Ukuvela ngaxeshanye akubalulekanga kuphela ekuveliseni izinambuzane kunye nokuzingisa kwabantu, kodwa nakubonelelo lwezinambuzane ezisele zikhulile, ezinokusetyenziswa njengokutya kwezilwanyana zasemanzini nezasemhlabeni (56).Ukuthintela ukuvela kwezithole kunokuchaphazela kakubi utshintshiselwano lokutya phakathi kwe-ecosystem yasemanzini kunye ne-ecosystem engaselunxwemeni, kwaye kusasaze iziphumo zongcoliseko lwasemanzini kwi-ecosystems yasemhlabeni (55, 56).Ukuncipha kobuninzi be-scrapers (izinambuzane ezitya i-algae) ezibonwe kuvavanyo lwe-meso-scale kubangele ukuhla kokusetyenziswa kwe-algae, okubangele ukwanda kwe-chlorophyll a (Umfanekiso 3).Le trophic cascade itshintsha i-carbon kunye ne-nitrogen fluxes kwiwebhu yokutya engamanzi, efana nophononongo oluvavanye iziphumo ze-pyrethroid bifenthrin kuluntu lwe-benthic (29).Ngoko ke, i-phenylpyrazoles, njenge-fipronil kunye neemveliso zayo zokuthotywa, i-pyrethroids, kunye mhlawumbi nezinye iintlobo ze-insecticide, zingakhuthaza ngokungangqalanga ukwanda kwe-algal biomass kunye nokuphazamiseka kwekhabhoni kunye ne-nitrogen kwimisinga emincinci.Ezinye iimpembelelo zinokunabela ekutshatyalalisweni komjikelo wekhabhoni kunye nenitrogen phakathi kwenkqubo yendalo yasemanzini neyasemhlabeni.
Ulwazi olufunyenwe kuvavanyo lwe-membrane oluphakathi luye lwasivumela ukuba sivavanye ukufaneleka kwe-ikholoji yoxinaniso lwe-fipronil ekhompawundi elinganiswe kwizifundo zenkalo ezinkulu eziqhutywe kwimimandla emihlanu yase-United States.Kwimifudlana emincinci engama-444, i-17% ye-concentration ye-avareji ye-fipronil compounds enye okanye ngaphezulu (i-avareji kwiiveki ze-4) idlule ixabiso le-HC5 elifunyenwe kuvavanyo lweendaba.Sebenzisa i-SSD ukusuka kumfuniselo we-meso-scale ukuguqula i-fipronil compound concentration kwi-toxicity-related index, oko kukuthi, isixa seeyunithi zetyhefu (ΣTUFipronils).Ixabiso le-1 libonisa ubutyhefu okanye ukuvezwa okuqokelelweyo kwekhompawundi ye-fipronil kudlula ukhuseleko olwaziwayo Iintlobo ezixabisa i-95%.Ubudlelwane obubalulekileyo phakathi kwe-ΣTUFipronil kwimimandla emine kwemihlanu kunye ne-SPEARpesticides isalathisi sempilo ye-invertebrate yoluntu ibonisa ukuba i-fipronil inokuchaphazela kakubi uluntu lwe-benthic invertebrate kwimilambo kwimimandla emininzi yase-United States.Ezi ziphumo zixhasa i-hypothesis kaWolfram et al.(3) Umngcipheko wezinambuzane ze-phenpyrazole kumanzi angaphezulu kwamanzi e-United States awuqondwa ngokupheleleyo ngenxa yokuba impembelelo kwizinambuzane zasemanzini yenzeka ngaphantsi komda wokulawula wangoku.
Uninzi lwemilambo enomxholo we-fipronil ngaphezulu komgangatho oyityhefu ibekwe kwindawo enedolophu ekumzantsi-mpuma (https://webapps.usgs.gov/rsqa/#!/region/SESQA).Uvavanyo lwangaphambili lwalo mmandla aluzange lugqibe nje ukuba i-fipronil iyona nto igxininisekileyo echaphazela i-invertebrate community structure kwi-creek, kodwa kunye ne-oksijeni ephantsi, i-oksijini edibeneyo, isondlo esikhulayo, utshintsho oluhambayo, ukuchithwa kwendawo yokuhlala, kunye nezinye izibulala-zinambuzane kunye nodidi olungcolileyo lubalulekile. umthombo woxinzelelo (57).Lo mxube weengxaki zoxinzelelo uhambelana "ne-syndrome yomlambo wedolophu", eyona nto ibonakaliso yendalo yomlambo ehlala ibonwa ngokumalunga nokusetyenziswa komhlaba wasezidolophini (58, 59).Iimpawu zokusetyenziswa komhlaba ezidolophini kwingingqi ekuMazantsi-mpuma ziyakhula kwaye kulindeleke ukuba zinyuke njengoko abantu balo mmandla bekhula.Impembelelo yophuhliso lwedolophu yexesha elizayo kunye nezibulali zinambuzane ekuqhubeni kwamanzi ezidolophini kulindeleke ukuba zande (4).Ukuba ukufudukela ezidolophini kunye nokusetyenziswa kwe-fipronil kuyaqhubeka nokukhula, ukusetyenziswa kwesi sibulali zinambuzane ezixekweni kunokuchaphazela ngakumbi uluntu.Nangona i-meta-analysis igqibezela ukuba ukusetyenziswa kwezibulali-zinambuzane kwezolimo kusongela i-ecosystems (2, 60), sicinga ukuba olu vavanyo luyijongela phantsi impembelelo yehlabathi jikelele yezibulali-zinambuzane ngokungaquki ukusetyenziswa kwedolophu.
Uxinzelelo oluhlukeneyo, olubandakanya i-pesticides, lunokuchaphazela uluntu lwe-macroinvertebrate kwiindawo eziphuhlisiwe zamanzi (idolophu, ezolimo kunye nokusetyenziswa komhlaba odibeneyo) kwaye inokuhambelana nokusetyenziswa komhlaba (58, 59, 61).Nangona olu phononongo lusebenzise isalathiso se-SPEARpesticides kunye neempawu zetyhefu ze-fipronil ezihlala emanzini ukuze kuncitshiswe impembelelo yezinto eziphazamisayo, ukusebenza kwesalathiso se-SPEARpesticides kunokuchatshazelwa kukuwohloka kwendawo yokuhlala, kwaye i-fipronil inokuthelekiswa nezinye ezinxulumene nePesticide (4, 17). 51, 57).Nangona kunjalo, imodeli yoxinzelelo oluninzi oluphuhliswe kusetyenziswa imilinganiselo yentsimi ukusuka kwizifundo ezimbini zokuqala zengingqi (eMidwestern kunye ne-Southeastern) ibonise ukuba i-pesticides yinto ebalulekileyo yoxinzelelo oluphezulu lweemeko zoluntu lwe-macroinvertebrate kwimilambo ejikelezayo.Kule mizekelo, iinguqu ezibalulekileyo ezichazayo ziquka izibulali-zinambuzane (ingakumbi i-bifenthrin), izondlo kunye neempawu zendawo yokuhlala kwiindawo ezininzi zezolimo eMidwest, kunye ne-pesticides (ingakumbi i-fipronil) kwiidolophu ezininzi ezisezantsi-mpuma.Utshintsho kwi-oksijeni, izondlo kunye nokuhamba (61, 62).Ngoko ke, nangona izifundo zengingqi zizama ukujongana nempembelelo yoxinzelelo lwe-non-pesticide kwiimpawu zokuphendula kunye nokulungelelanisa izikhombisi zokuchaza impembelelo ye-fipronil, iziphumo zentsimi zolu vavanyo zixhasa umbono we-fipronil.) Kufuneka kuthathwe njengenye yezona mithombo zinempembelelo kwimilambo yaseMelika, ngakumbi kumzantsi-mpuma weUnited States.
Ukwenzeka kokuthotywa kwezibulali zinambuzane kwindawo engqongileyo akufane kubhalwe, kodwa isoyikiso kwizinto eziphilayo zasemanzini zinokuba yingozi ngakumbi kunomzimba womzali.Kwimeko ye-fipronil, izifundo zentsimi kunye novavanyo lwe-meso-scale lubonise ukuba iimveliso zokuthotywa zixhaphake njengomzimba womzali kwimijelo yesampuli kwaye zinetyhefu efanayo okanye ephezulu (Itheyibhile 1).Kulingelo lwenwebu ephakathi, i-fluorobenzonitrile sulfone yayiyeyona tyhefu yeemveliso zokuthotywa kwezibulali-zinambuzane ezifundisiweyo, kwaye yayinetyhefu ngakumbi kunekhompawundi yomzali, kwaye yabhaqwa ngamaxesha amaninzi afana nalawo ekhompawundi yomzali.Ukuba ngaba amayeza okubulala izitshabalalisi alinganiswa kuphela, iziganeko zetyhefu ezinokuthi zingaqatshelwa, kwaye ukunqongophala kolwazi lwetyhefu ngexesha lokuthotywa kwezitshabalalisi kuthetha ukuba ukwenzeka kwazo kunye neziphumo zinokungahoywa.Umzekelo, ngenxa yokunqongophala kolwazi malunga netyhefu yeemveliso zokonakala, uvavanyo olubanzi lwezitshabalalisi kwimisinga yaseSwitzerland lwenziwa, kubandakanywa ne-134 yeemveliso zokuthotywa kwe-pesticide, kwaye yikhompawundi yomzali kuphela eyaqwalaselwa njengekhompawundi yomzali kuvavanyo lwayo lwe-ecotoxicological risk.
Iziphumo zolu vavanyo lomngcipheko we-ikholoji zibonisa ukuba iikhompawundi ze-fipronil zineziphumo ezibi kwimpilo yomlambo, ngoko kunokucingelwa ukuba iziphumo ezibi zinokubonwa naphi na apho i-fipronil ikhompawundi idlula inqanaba le-HC5.Iziphumo zovavanyo lwe-mesoscopic zizimele kwindawo, zibonisa ukuba ukuxinana kwe-fipronil kunye neemveliso zayo zokuthotywa kwi-tax ye-stream ezininzi ziphantsi kakhulu kunokuba zirekhodwe ngaphambili.Sikholelwa ukuba oku kufunyaniswayo kunokwenzeka ukuba kwandiswe kwiprotobiota kwimisinga ecocekileyo naphi na.Iziphumo zovavanyo lwe-meso-scale ziye zasetyenziswa kwizifundo zentsimi ezinkulu (444 imijelo emincinci equlunqwe lusetyenziso oluxubeneyo lwasezidolophini, ezolimo, kunye nomhlaba kwimimandla emihlanu emikhulu eUnited States), kwaye kwafunyaniswa ukuba ukuxinana kwemijelo emininzi. apho i-fipronil ichongiwe kulindeleke ukuba ibekho Ubukho betyhefu bucebisa ukuba ezi ziphumo zinganabela kwamanye amazwe apho i-fipronil isetyenziswa khona.Ngokweengxelo, inani labantu abasebenzisa iFipronil liyanda eJapan, e-UK nase-US (7).I-Fipronil ikhona phantse kuwo onke amazwekazi, kuquka i-Australia, uMzantsi Melika kunye ne-Afrika (https://coherentmarketinsights.com/market-insight/fipronil-market-2208).Iziphumo zophononongo lwe-meso-to-field oluthiwe thaca apha lubonisa ukuba ukusetyenziswa kwe-fipronil kunokuba nokubaluleka kwendalo kwihlabathi liphela.
Ukufumana imathiriyeli eyongezelelweyo yeli nqaku, nceda ubone http://advances.sciencemag.org/cgi/content/full/6/43/eabc1299/DC1
Eli linqaku elivulekileyo lokufikelela elisasazwa phantsi kwemigaqo ye-Creative Commons Attribution-Non-Commercial License, evumela ukusetyenziswa, ukuhanjiswa kunye nokuveliswa kwakhona kuyo nayiphi na indlela, nje kuphela ukuba ukusetyenziswa kokugqibela kungekhona inzuzo yorhwebo kwaye isiseko kukuba umsebenzi wokuqala uchanekile.Isalathiso.
Qaphela: Sikucela kuphela ukuba usinike idilesi ye-imeyile ukuze umntu omcebisayo kwiphepha azi ukuba ufuna ukubona i-imeyile kwaye ayingospam.Asiyi kubamba naziphi na iidilesi ze-imeyile.
Lo mbuzo usetyenziselwa ukuvavanya ukuba ngaba ungumtyeleli kwaye uthintele ukuthunyelwa kwe-spam okuzenzekelayo.
UJanet L. Miller, uTravis S. Schmidt, uPeter C. Van Metre, uBarbara Mahler ( uBarbara J. Mahler, uMark W. Sandstrom, uLisa H. Nowell, uDaren M. Carlisle, uPatrick W. Moran
Uphononongo lubonise ukuba izibulali-zinambuzane eziqhelekileyo ezifunyanwa rhoqo kwimisinga yaseMelika zinetyhefu ngakumbi kunokuba bekucingelwa ngaphambili.
UJanet L. Miller, uTravis S. Schmidt, uPeter C. Van Metre, uBarbara Mahler ( uBarbara J. Mahler, uMark W. Sandstrom, uLisa H. Nowell, uDaren M. Carlisle, uPatrick W. Moran
Uphononongo lubonise ukuba izibulali-zinambuzane eziqhelekileyo ezifunyanwa rhoqo kwimisinga yaseMelika zinetyhefu ngakumbi kunokuba bekucingelwa ngaphambili.
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