Mankhwala ophera tizilombo m'mitsinje akukhala nkhawa kwambiri padziko lonse lapansi, koma pali chidziwitso chochepa chokhudza chitetezo chazamoyo zam'madzi.Pakuyesa kwa masiku 30 kwa mesocosmic, zamoyo zam'madzi za benthic zam'madzi zidakumana ndi mankhwala wamba a fipronil ndi mitundu inayi ya zinthu zowononga.Gulu la fipronil lidayambitsa kusintha kwa katulutsidwe ndi trophic cascade.Kuphatikizika kothandiza (EC50) komwe fipronil ndi sulfide, sulfone ndi desulfinyl degradation mankhwala zimapangitsa 50% kuyankha kwapangidwa.Misonkho sagwirizana ndi fipronil.Kuphatikizika kwangozi kwa 5% ya mitundu yomwe yakhudzidwa kuchokera pamiyezo 15 ya mesocosmic EC50 imagwiritsidwa ntchito kutembenuza kuchuluka kwa fipronil m'munda kukhala kuchuluka kwa mayunitsi oopsa (∑TUFipronils).Mu 16% ya mitsinje yotengedwa kuchokera ku maphunziro asanu a m'madera, pafupifupi ∑TUFipronil inaposa 1 (zimasonyeza kawopsedwe).Zizindikiro za invertebrate za zamoyo zomwe zili pachiwopsezo zimayenderana moyipa ndi TUTUipronil m'malo anayi mwa asanu a zitsanzo.Kuwunika kwachiwopsezo kwachilengedweku kukuwonetsa kuti kuchepa kwamafuta a fipronil kumachepetsa midzi yambiri m'madera ambiri a United States.
Ngakhale kupanga mankhwala opangidwa kwachulukirachulukira m'zaka zaposachedwa, kukhudzika kwa mankhwalawa pazachilengedwe zomwe sizinali zomwe akufuna sikunamveke bwino (1).M'madzi apamtunda pomwe 90% ya minda yapadziko lonse lapansi imatayika, palibe chidziwitso chokhudza mankhwala ophera tizilombo, koma pomwe pali deta, nthawi yoti mankhwala ophera tizilombo apitirire malire ndi theka (2).Kuwunika kwa meta kwa mankhwala ophera tizilombo m'madzi ku United States kunapeza kuti 70% ya malo ochitira zitsanzo, mankhwala ophera tizilombo amapitilira malire (3).Komabe, kuwunika kwa meta (2, 3) kumangoyang'ana pamadzi apamtunda omwe amakhudzidwa ndikugwiritsa ntchito nthaka yaulimi, ndipo ndi chidule cha maphunziro apadera.Mankhwala ophera tizilombo, makamaka ophera tizirombo, amapezekanso kwambiri m'ngalande za m'matauni (4).Ndikosowa kuchita kafukufuku wokwanira wa mankhwala ophera tizilombo m'madzi a pamwamba omwe amachotsedwa ku ulimi ndi madera akumidzi;motero, sizikudziwika ngati mankhwala ophera tizilombo amawopseza kwambiri madzi apansi panthaka komanso kukhulupirika kwawo kwachilengedwe.
Benzopyrazoles ndi neonicotinoids adakhala gawo limodzi mwa magawo atatu a msika wapadziko lonse wopha tizilombo mu 2010 (5).M'madzi apamtunda ku United States, fipronil ndi zinthu zake zowonongeka (phenylpyrazoles) ndizo mankhwala ophera tizilombo, ndipo kuchuluka kwawo nthawi zambiri kumaposa miyezo ya m'madzi (6-8).Ngakhale ma neonicotinoids akopa chidwi chifukwa cha zotsatira zake pa njuchi ndi mbalame komanso kuchuluka kwawo (9), fipronil ndi poizoni kwambiri ku nsomba ndi mbalame (10), pomwe ma phenylpyrazoles Class mankhwala amakhala ndi herbicidal effect (5).Fipronil ndi mankhwala ophera tizilombo omwe amagwiritsidwa ntchito polimbana ndi tizirombo m'matawuni ndi ulimi.Popeza fipronil adalowa msika wapadziko lonse mu 1993, kugwiritsa ntchito fipronil ku United States, Japan ndi United Kingdom kwakula kwambiri (5).Ku United States, fipronil imagwiritsidwa ntchito polimbana ndi nyerere ndi chiswe, ndipo imagwiritsidwa ntchito ku mbewu monga chimanga (kuphatikiza mankhwala a mbewu), mbatata ndi minda ya zipatso (11, 12).Kugwiritsa ntchito kwaulimi kwa fipronil ku United States kudakwera kwambiri mu 2002 (13).Ngakhale kuti palibe deta yogwiritsira ntchito m’matauni ya dziko lonse imene ikupezeka, kugwiritsidwa ntchito m’matauni ku California kunakwera kwambiri mu 2006 ndi 2015 (https://calpip.cdpr.ca) .gov/main .cfm, yofikira pa Disembala 2, 2019).Ngakhale kuchuluka kwa fipronil (6.41μg/L) kumapezeka m'mitsinje m'madera ena aulimi omwe amagwiritsidwa ntchito kwambiri (14), poyerekeza ndi mitsinje yaulimi, mitsinje yakumidzi ku United States nthawi zambiri imakhala yodziwika bwino komanso yokwera kwambiri, yabwino kwa kuchitika kwa mkuntho kumalumikizidwa ndi mayeso (6, 7, 14-17).
Fipronil imalowa m'chilengedwe chamadzi othamanga kapena madontho kuchokera m'nthaka kulowa mumtsinje (7, 14, 18).Fipronil imakhala ndi kusungunuka kochepa (lamulo la Henry nthawi zonse 2.31 × 10-4 Pa m3 mol-1), kusungunuka kwamadzi pang'ono (3.78 mg / l pa 20 ° C), ndi hydrophobicity yapakati (log Kow ndi 3.9 mpaka 4.1) kuyenda m'nthaka kumakhala kochepa kwambiri (log Koc ndi 2.6 mpaka 3.1) (12, 19), ndipo imawonetsa kusakhazikika kwachilengedwe (20).Finazepril imawonongeka ndi photolysis, oxidation, pH-dependent hydrolysis ndi kuchepetsa, kupanga zinthu zinayi zazikulu zowonongeka: dessulfoxyphenapril (kapena sulfoxide), phenaprenip sulfone (sulfone), Filofenamide (amide) ndi filofenib sulfide (sulfide).Zowonongeka za Fipronil zimakonda kukhala zokhazikika komanso zolimba kuposa zopangira makolo (21, 22).
Kawopsedwe ka fipronil ndi kuwonongeka kwake kukhala mitundu yosakhala ndi zolinga (monga zam'madzi zopanda msana) zalembedwa bwino (14, 15).Fipronil ndi mankhwala a neurotoxic omwe amasokoneza njira ya chloride ion kudzera munjira ya chloride yoyendetsedwa ndi gamma-aminobutyric acid mu tizirombo, zomwe zimapangitsa kuti pakhale kukhazikika kokwanira kudzetsa chisangalalo komanso kufa kwambiri (20).Fipronil ndi poyizoni wosankha, motero imakhala ndi mgwirizano wolumikizana ndi tizilombo kuposa nyama zoyamwitsa (23).Ntchito yophera tizilombo ya zinthu zowonongeka za fipronil ndizosiyana.Kawopsedwe wa sulfone ndi sulfide ku zamoyo zam'madzi am'madzi ndi ofanana kapena apamwamba kuposa a pawiri ya makolo.Desulfinyl ili ndi kawopsedwe kakang'ono koma ndi kawopsedwe kakang'ono kuposa kawopsedwe ka makolo.Zopanda poizoni (23, 24).Kutengeka kwa zamoyo zam'madzi zam'madzi ku kuwonongeka kwa fipronil ndi fipronil kumasiyanasiyana mkati ndi pakati pa taxa (15), ndipo nthawi zina kumapitilira kuyitanitsa (25).Pomaliza, pali umboni wosonyeza kuti phenylpyrazoles ndi poizoni kwambiri ku chilengedwe kuposa momwe amaganizira kale (3).
Ma benchmarks achilengedwe a m'madzi potengera kuyezetsa kawopsedwe ka mu labotale angachepetse chiwopsezo cha anthu akumunda (26-28).Miyezo ya m'madzi nthawi zambiri imakhazikitsidwa ndi mtundu umodzi woyesera kawopsedwe wa labotale pogwiritsa ntchito mtundu umodzi kapena zingapo zopanda msana za m'madzi (mwachitsanzo, Diptera: Chironomidae: Chironomus ndi Crustacea: Daphnia magna ndi Hyalella azteca).Zamoyo zoyesazi nthawi zambiri zimakhala zosavuta kulima kuposa nyama zina za benthic macroinvertebrates (mwachitsanzo, phe genus::), ndipo nthawi zina sizikhudzidwa kwambiri ndi zowononga.Mwachitsanzo, D. Magna sakhudzidwa kwambiri ndi zitsulo zambiri kusiyana ndi tizilombo tina, pamene A. zteca sakhudzidwa kwambiri ndi pyrethroid insecticide bifenthrin kusiyana ndi kukhudzidwa kwake ndi nyongolotsi (29, 30).Kuchepetsa kwina kwa ma benchmark omwe alipo ndi mathero omwe amagwiritsidwa ntchito powerengera.Zizindikiro zodziwika bwino zimatengera kufa (kapena kukhazikika kwa crustaceans), pomwe ma benchmark osatha nthawi zambiri amatengera malekezero ang'onoang'ono (monga kukula ndi kubereka) (ngati alipo).Komabe, pali zowopsa zomwe zimachulukirachulukira, monga kukula, kutuluka, kufa ziwalo, ndi kuchedwa kwachitukuko, zomwe zingakhudze kupambana kwa misonkho ndi zochitika zamagulu.Zotsatira zake, ngakhale chizindikirochi chimapereka maziko a kufunikira kwachilengedwe kwachilengedwe, kufunika kwa chilengedwe monga poyambira pachiwopsezo sikudziwika.
Kuti mumvetse bwino zotsatira za mankhwala a fipronil pa zamoyo zam'madzi za benthic (zopanda msana ndi algae), magulu achilengedwe a benthic adabweretsedwa mu labotale ndipo adakumana ndi zosokoneza panthawi ya 30-day flow Fipronil kapena imodzi mwa mayesero anayi owononga fipronil.Cholinga cha kafukufuku ndi kupanga mitundu yeniyeni ya 50% (mtengo wa EC50) pamtundu uliwonse wa fipronil woimira msonkho waukulu wa mtsinje, ndi kudziwa momwe zinthu zowononga zimakhudzira chikhalidwe ndi ntchito za anthu [ie, ndende ya zoopsa] 5 % Ya mitundu yomwe yakhudzidwa (HC5) ndi zotsatira zosalunjika monga kusintha kwa kawonekedwe ndi trophic dynamics].Kenako malire (mtengo wokhazikika wa HC5) wopezedwa kuchokera ku kuyesa kwa mesoscopic adagwiritsidwa ntchito kumunda wotengedwa ndi United States Geological Survey (USGS) kuchokera kumadera asanu a United States (Northeast, Southeast, Midwest, Northwest Pacific, and Central California). Deta ya Coastal Zone) monga gawo la zowunika zamtundu wa USGS (https://webapps.usgs.gov/rsqa/#!/).Monga tikudziwira, uku ndiko kuyesa koyamba kwa chiwopsezo cha chilengedwe.Imafufuza mozama zotsatira za mankhwala a fipronil pazamoyo zomwe zimayendetsedwa ndi maso-chilengedwe, ndiyeno imagwiritsa ntchito zotsatilazi pakuwunika kwamagawo a continental.
Kuyesa kwa masiku 30 kwa mesocosmic kudachitika ku USGS Aquatic Laboratory (AXL) ku Fort Collins, Colorado, USA kuyambira Okutobala 18th mpaka Novembara 17th, 2017, kwa tsiku limodzi lanyumba ndi masiku 30 akuyesa.Njirayi idafotokozedwa kale (29, 31) ndikufotokozedwa mwatsatanetsatane muzowonjezera.Malo a meso ali ndi maulendo 36 oyendayenda mumayendedwe anayi omwe akugwira ntchito (matangi amadzi ozungulira).Mtsinje uliwonse wamoyo uli ndi chozizirira kuti madzi asatenthedwe ndipo amawunikira ndi 16:8 kuwala kwamdima.Kuthamanga kwa meso-level ndi chitsulo chosapanga dzimbiri, chomwe chili choyenera hydrophobicity ya fipronil (log Kow = 4.0) ndi yoyenera kuyeretsa zosungunulira za organic (Chithunzi S1).Madzi omwe amagwiritsidwa ntchito poyesa maso-scale adatengedwa kuchokera kumtsinje wa Cache La Poudre (magwero akumtunda kuphatikiza Rocky Mountain National Park, National Forest ndi Continental Divide) ndikusungidwa m'matanki anayi osungira a polyethylene a AXL.Kuwunika kwam'mbuyo kwa sediment ndi madzi omwe adasonkhanitsidwa pamalowa sikunapeze mankhwala ophera tizilombo (29).
Mapangidwe oyesera a meso-scale amakhala ndi mitsinje 30 yokonza ndi mitsinje 6 yowongolera.Mtsinje wochizira umalandira madzi oyeretsedwa, omwe ali ndi mawonekedwe osasinthika amafuta a fipronil: fipronil (fipronil (Sigma-Aldrich, CAS 120068-37-3), amide (Sigma-Aldrich, CAS 205650-69-7), gulu la desulfurization [US Environmental Protection Agency (EPA) Library ya Pesticide, CAS 205650-65-3], sulfone (Sigma-Aldrich, CAS 120068-37-2) ndi sulfide (Sigma-Aldrich, CAS 120067-83-6); chiyero chonse ≥ 97.8%. Malinga ndi zomwe zafalitsidwa (7, 15, 16, 18, 21, 23, 25, 32, 33). Mwa kusungunula fipronil pawiri mu methanol (Thermo Fisher Scientific, American Chemical Society certification level), ndi kuchepetsa Chifukwa kuchuluka kwa methanol pa mlingo ndi kosiyana, m'pofunika kuwonjezera methanol pa mitsinje yonse ya mankhwala ngati pakufunika. 0.05 ml/L) m'mitsinje Mawonedwe apakati a mitsinje ina itatu yolamulira adalandira madzi a m'mitsinje opanda methanol, apo ayi amatengedwa ngati mitsinje ina yonse.
Patsiku lachisanu ndi chitatu, tsiku la 16 ndi tsiku la 26, kutentha, pH mtengo, mphamvu zamagetsi ndi kuwonongeka kwa fipronil ndi fipronil zinayesedwa mu membrane yothamanga.Pofuna kutsata kuwonongeka kwa fipronil ya kholo panthawi yoyesa ma TV, fipronil (makolo) adagwiritsidwa ntchito pochiza matumbo a m'mimba kwa masiku atatu [masiku 5, 12 ndi 21 (n = 6)] chifukwa cha kutentha, pH , Conductivity, fipronil ndi fipronil degradation sampling.Zitsanzo zowunikira mankhwala ophera tizilombo zidasonkhanitsidwa ndikusefa 10 ml ya madzi oyenda mu 20 ml amber glass vial kudzera mu sefa ya syringe ya Whatman 0.7-μm GF/F yokhala ndi singano yayikulu.Zitsanzozi zidawumitsidwa nthawi yomweyo ndikutumizidwa ku USGS National Water Quality Laboratory (NWQL) ku Lakewood, Colorado, USA kuti iunikenso.Pogwiritsa ntchito njira yowongoleredwa ya njira yomwe idasindikizidwa kale, Fipronil ndi zinthu zowononga 4 mu zitsanzo zamadzi zidatsimikiziridwa ndi jakisoni wamadzimadzi mwachindunji (DAI) liquid chromatography-tandem mass spectrometry (LC-MS / MS; Agilent 6495).Mulingo wozindikira zida (IDL) akuyerekezeredwa kukhala mulingo wocheperako womwe umakwaniritsa mulingo wozindikiritsa;IDL ya fipronil ndi 0.005 μg/L, ndipo IDL ya fipronil inayi ndi 0.001 μg/L.Zowonjezerazo zimapereka kufotokozera kwathunthu kwa njira zomwe zimagwiritsidwa ntchito poyesa mankhwala a fipronil, kuphatikizapo kuwongolera khalidwe ndi njira zotsimikizira (mwachitsanzo, kuchira kwachitsanzo, ma spikes, kufufuza kwa gulu lachitatu, ndi zomwe zikusowekapo).
Pamapeto pa kuyesera kwa Mesocosmic kwa masiku a 30, kuwerengera ndi kuzindikiritsa anthu akuluakulu ndi mphutsi zopanda msana zinamalizidwa (mapeto ake osonkhanitsa deta).Akuluakulu omwe akutuluka amatengedwa kuchokera muukonde tsiku lililonse ndikuwumitsidwa mu chubu choyera cha 15 ml Falcon centrifuge.Pamapeto pa kuyesera (tsiku la 30), zomwe zili mu nembanemba mumtsinje uliwonse zidatsukidwa kuti zichotse zamoyo zilizonse, ndikusefa (250 μm) ndikusungidwa mu 80% ethanol.Timberline Aquatics (Fort Collins, CO) yatsiriza kuzindikiritsa mphutsi za mphutsi ndi zazikulu zopanda msana mpaka kutsika kwambiri kwa taxonomic kotheka, kawirikawiri mitundu.Pa masiku 9, 19 ndi 29, chlorophyll a ankayezedwa katatu mu mesoscopic nembanemba wa mtsinje uliwonse.Zambiri zamakina ndi zachilengedwe monga gawo la kuyesa kwa mesoscopic zimaperekedwa pakutulutsidwa kwa data komweku (35).
Kafukufuku wa zachilengedwe anachitidwa m’mitsinje ing’onoing’ono (yoyenda) m’madera akuluakulu asanu a United States, ndipo mankhwala ophera tizilombo ankayang’aniridwa m’nthaŵi yachilolezo yapitayi.Mwachidule, pogwiritsa ntchito nthaka yaulimi ndi midzi (36-40), 77 ku malo a 100 anasankhidwa m'dera lililonse (malo 444 onse).M'nyengo yamasika ndi chilimwe cha chaka chimodzi (2013-2017), zitsanzo za madzi zimasonkhanitsidwa kamodzi pa sabata m'dera lililonse kwa masabata 4 mpaka 12.Nthawi yeniyeni imadalira dera komanso kukula kwachitukuko.Komabe, masiteshoni 11 kudera lakumpoto chakum’mawa ali pafupifupi m’mphepete mwa madzi.Palibe chitukuko, kupatula kuti chitsanzo chimodzi chokha chinasonkhanitsidwa.Popeza kuti nthawi zowunikira mankhwala ophera tizilombo m'maphunziro a m'madera ndizosiyana, kuyerekeza, zitsanzo zinayi zokha zomaliza zomwe zasonkhanitsidwa pamalo aliwonse zimaganiziridwa pano.Zikuganiziridwa kuti chitsanzo chimodzi chosonkhanitsidwa kumalo osatukuka kumpoto chakum'mawa (n = 11) chikhoza kuimira nthawi ya masabata 4.Njirayi imatsogolera ku chiwerengero chofanana cha kuwonetsetsa kwa mankhwala ophera tizilombo (kupatula malo a 11 kumpoto chakum'mawa) ndi nthawi yofanana;akukhulupirira kuti masabata 4 ndiatali wokwanira kuti adziwonetsere kwa nthawi yayitali ku biota, koma afupi kwambiri kuti chilengedwe sichiyenera kuchira kuchokera kuzinthu izi.
Pankhani ya kuyenda kokwanira, chitsanzo cha madzi chimasonkhanitsidwa ndi kuthamanga kosalekeza ndi kuwonjezereka kwa m'lifupi kosalekeza (41).Pamene otaya sikokwanira kugwiritsa ntchito njira imeneyi, mukhoza kusonkhanitsa zitsanzo ndi kusakanikirana kwambiri zitsanzo kapena tagwira kuchokera pakati pa mphamvu yokoka otaya.Gwiritsani ntchito syringe yoboola kwambiri ndi sefa ya chimbale (0.7μm) kuti mutenge 10 ml ya zitsanzo zosefedwa (42).Kupyolera mu DAI LC-MS/MS/MS/MS, zitsanzo za madzi zinawunikidwa pa NWQL kwa 225 mankhwala ophera tizilombo ndi zinthu zowononga tizilombo, kuphatikizapo fipronil ndi 7 degradation products (dessulfinyl fipronil, fipronil) Sulfides, fipronil sulfone, deschlorofipronil, fipronil, fipronil, fipronil, fipronil ndi fipronil).).Miyezo yocheperako yoperekera malipoti pamaphunziro akumunda ndi: fipronil, desmethylthio fluorobenzonitrile, fipronil sulfide, fipronil sulfone, ndi deschlorofipronil 0.004 μg/L;dessulfinyl fluorfenamide ndi Kuchuluka kwa fipronil amide ndi 0.009 μg/lita;kuchuluka kwa fipronil sulfonate ndi 0.096 μg/lita.
Madera a invertebrates amayesedwa kumapeto kwa kafukufuku wa dera lililonse (kasupe/chilimwe), nthawi zambiri nthawi imodzi ndi zomwe zidachitika pomaliza kuyesa mankhwala ophera tizilombo.Nyengo yakukula ikatha komanso kugwiritsa ntchito kwambiri mankhwala ophera tizilombo, nthawi yotsatsira zisankho iyenera kukhala yogwirizana ndi kutsika kochepa, ndipo kuyenera kugwirizana ndi nthawi yomwe gulu la nyama zopanda fupa la mtsinje limakhwima ndipo limakhala makamaka pa moyo wa mphutsi.Pogwiritsa ntchito sampuli ya Surber yokhala ndi mauna a 500μm kapena ukonde wa D-frame, sampuli yamtundu wa invertebrate idamalizidwa mu 437 mwa masamba 444.Njira yochitira sampuli ikufotokozedwa mwatsatanetsatane muzowonjezera.Pa NWQL, zamoyo zonse zopanda msana nthawi zambiri zimadziwika ndikulembedwa pamtundu wamtundu kapena mitundu.Zambiri zamakina ndi zachilengedwe zomwe zasonkhanitsidwa m'gawoli ndikugwiritsidwa ntchito m'mawu apamanjawa zitha kupezeka pakutulutsa komweku (35).
Pamagulu asanu a fipronil omwe amagwiritsidwa ntchito poyesa masoscopic, kuchuluka kwa ma invertebrates a mphutsi kuchepetsedwa ndi 20% kapena 50% kunawerengedwa poyerekezera ndi kulamulira (ie EC20 ndi EC50).Deta [x = yolemera nthawi ya fipronil concentration (onani zowonjezera zowonjezera kuti mumve zambiri), y = larval abundance kapena ma metrics ena] adayikidwa pa phukusi la R(43) lowonjezera pogwiritsa ntchito njira ya katatu ya logarithmic regression" drc".Mphepete mwake amakwanira zamoyo zonse (mphutsi) ndi kuchuluka kokwanira ndipo amakumana ndi zokonda zina (mwachitsanzo, kulemera kwa taxa, kuchuluka kwa mayfly, ndi kuchuluka kwathunthu) kuti mumvetsetse bwino zomwe zimachitika mdera.Nash-Sutcliff coefficient (45) imagwiritsidwa ntchito poyesa kukwanira kwachitsanzo, komwe kusakwanira bwino kwachitsanzo kumatha kulandira zinthu zopanda malire, ndipo mtengo wokwanira bwino ndi 1.
Kufufuza zotsatira za mankhwala a fipronil pa kutuluka kwa tizilombo mukuyesera, deta inayesedwa m'njira ziwiri.Choyamba, pochotsa mawonekedwe apakati a kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe ka kayendetsedwe kake.Konzani mfundo izi motsutsana ndi nthawi kuti mumvetsetse kupatuka kwa mkhalapakati wamadzimadzi kuchokera kwa mkhalapakati wamadzimadzi pakuyesa kwa masiku 30.Chachiwiri, werengera kuchuluka kwa zochitika zonse za mesophyll iliyonse yotuluka, yomwe imatanthauzidwa ngati chiŵerengero cha chiwerengero cha mesophyll mumayendedwe operekedwa ku chiwerengero cha mphutsi ndi akuluakulu omwe ali mu gulu lolamulira, ndipo ndi yoyenera kubwereza katatu kwa logarithmic regression. .Tizilombo tonse tomera tomwe tinasonkhanitsidwa tidachokera m'mabanja ang'onoang'ono awiri a banja la Chironomidae, kotero kuwunika kophatikizana kudachitika.
Kusintha kwa chikhalidwe cha anthu, monga kutayika kwa msonkho, pamapeto pake kungadalire zotsatira zachindunji kapena zosalunjika za zinthu zapoizoni, ndipo zingayambitse kusintha kwa ntchito za dera (mwachitsanzo, trophic cascade).Kuyesa kuphulika kwa trophic, maukonde osavuta adawunikidwa pogwiritsa ntchito njira yowunikira njira (R phukusi "piecewiseSEM") (46).Kwa zoyesera za mesoscopic, zimaganiziridwa kuti fipronil, desulfinyl, sulfide ndi sulfone (osayesedwa amide) m'madzi kuti achepetse zotsalira za scraper, mosadziwika bwino zimatsogolera pakuwonjezeka kwa biomass ya chlorophyll a (47).Kuphatikizika kwapawiri ndizomwe zimasinthiratu, ndipo scraper ndi chlorophyll biomass ndizomwe zimayankha.Chiwerengero cha Fisher's C chimagwiritsidwa ntchito poyesa kukwanira kwamitundu, kuti mtengo wa P <0.05 uwonetse kukwanira kwachitsanzo (46).
Kuti akhazikitse njira yodzitetezera pachiwopsezo cha eco-community, gawo lililonse lapeza 95% ya mitundu yomwe yakhudzidwa (HC5) kugawa kwamtundu wamtundu wamtundu (SSD) komanso chitetezo changozi.Maseti atatu a data a SSD adapangidwa: (i) seti ya data yokha, (ii) seti ya data yomwe ili ndi data yonse ya meso ndi data yosonkhanitsidwa kuchokera ku funso la database la EPA ECOTOX (https://cfpub.epa.gov/ecotox) /, lofikira pa March 14, 2019), nthawi yophunzira ndi masiku 4 kapena kupitilira apo, ndipo (iii) seti ya data yomwe ili ndi data yonse ya mesoscopic ndi data ya ECOTOX, momwe data ya ECOTOX (kuwonetseredwa modzidzimutsa) yogawidwa movutirapo ndi The ratio of chronic D. magna ( 19.39) kufotokoza kusiyana kwa nthawi yowonekera ndikuyerekeza mtengo wa EC50 (12).Cholinga chathu chopanga mitundu ingapo ya ma SSD ndi (i) kupanga ma HC5 kuti afananize ndi data yakumunda (yokha ya ma SSD a media), ndi (ii) kuwunika kuti media media ndiyovomerezeka kwambiri kuposa mabungwe owongolera kuti aphatikizidwe muzamoyo zam'madzi. kulimba kwa ma benchmarks a moyo ndi kukhazikitsidwa kwanthawi zonse kwazinthu za data, motero kuthekera kogwiritsa ntchito maphunziro a mesoscopic pakusintha.
SSD idapangidwa pa seti iliyonse pogwiritsa ntchito phukusi la R "ssdtools" (48).Gwiritsani ntchito bootstrap (n = 10,000) kuti muyerekeze HC5 avareji ndi nthawi yodalirika (CI) kuchokera ku SSD.Mayankho amisonkho makumi anayi mphambu asanu ndi anayi (onse omwe adadziwika kuti ndi mtundu kapena mitundu) opangidwa kudzera mu kafukufukuyu aphatikizidwa ndi mayankho 32 amisonkho omwe adapangidwa kuchokera kumaphunziro asanu ndi limodzi omwe adasindikizidwa munkhokwe ya ECTOX, pakuyankha kwa Misonkho 81 kungagwiritsidwe ntchito pakukula kwa SSD. .Popeza palibe deta yomwe inapezeka mu nkhokwe ya ECOTOX ya amides, palibe SSD yomwe inapangidwira ma amides ndipo yankho limodzi lokha la EC50 linapezedwa kuchokera ku kafukufuku wamakono.Ngakhale mtengo wa EC50 wa gulu limodzi lokha la sulfide udapezeka mu database ya ECOTOX, wophunzira yemwe wamaliza maphunzirowa ali ndi 12 EC50.Choncho, ma SSD a magulu a sulfnyl apangidwa.
Miyezo yeniyeni ya HC5 yamafuta a fipronil omwe adapezedwa kuchokera ku data ya SSD ya Mesocosmos okha adaphatikizidwa ndi deta yakumunda kuti awone kuwonekera komanso kuwopsa kwa mankhwala a fipronil m'mitsinje 444 kuchokera kumadera asanu ku United States.Pazenera lachitsanzo la masabata 4 omaliza, kuchuluka kulikonse kwamafuta a fipronil omwe apezeka (kuchuluka kosazindikirika ndi ziro) kumagawidwa ndi HC5 yake, ndipo chiŵerengero cha pawiri cha chitsanzo chilichonse chikuphatikizidwa kuti mupeze The total toxicity unit of fipronil (ΣTUFipronils), kumene ΣTUFipronils> 1 amatanthauza kawopsedwe.
Poyerekeza kuchuluka kwa ngozi kwa 50% ya zamoyo zomwe zakhudzidwa (HC50) ndi mtengo wa EC50 wa chuma cha taxa chochokera ku kuyesa kwa membrane wapakatikati, SSD yotengedwa kuchokera ku data ya membala wapakatikati idawunikidwa kuti iwonetse chidwi cha chilengedwe chazachilengedwe ku fipronil. digiri..Kupyolera mu kuyerekezera uku, kusasinthasintha pakati pa njira ya SSD (kuphatikiza okhawo taxa omwe ali ndi mgwirizano woyankha mlingo) ndi njira ya EC50 (kuphatikizapo msonkho wapadera womwe umawonedwa pakati pa danga) pogwiritsa ntchito njira ya EC50 yoyezera kulemera kwa taxa ikhoza kuyesedwa Kugonana.Chiyanjano cha mayankho a mlingo.
Chizindikiro chamtundu wa mankhwala ophera tizilombo (SPEARpesticides) chinawerengedwa kuti chifufuze ubale womwe ulipo pakati pa thanzi la anthu osabala msana ndi ΣTUFipronil mu mitsinje 437 yosonkhanitsa invertebrates.Ma metric a SPEARpesticides amasintha kapangidwe ka zamoyo zopanda msana kukhala zochulukira za taxonomy yachilengedwe yokhala ndi mawonekedwe achilengedwe ndi zachilengedwe, motero zimapatsa chidwi ku mankhwala ophera tizilombo.Chizindikiro cha SPEARpesticides sichimakhudzidwa ndi ma covariate achilengedwe (49, 50), ngakhale magwiridwe ake adzakhudzidwa ndi kuwonongeka kwakukulu kwa malo (51).Zambiri zomwe zimasonkhanitsidwa patsamba la msonkho uliwonse zimagwirizanitsidwa ndi mtengo wofunikira wa msonkho wokhudzana ndi pulogalamu ya ASTERICS kuti awone momwe mtsinjewu ulili (https://gewaeser-bewertung-berechnung.de/index.php/home html).Kenako lowetsani deta mu Indicate (http://systemecology.eu/indicate/) software (mtundu 18.05).Mu pulogalamu iyi, nkhokwe yaku Europe ndi malo osungira omwe ali ndi chidwi ndi thupi ku mankhwala ophera tizilombo amagwiritsidwa ntchito kusintha zomwe zapezeka patsamba lililonse kukhala chizindikiro cha SPEARpesticides.Lililonse mwa maphunziro asanu a m'maderawa adagwiritsa ntchito General Additive Model (GAM) ["mgcv" phukusi mu R(52)) kuti afufuze mgwirizano pakati pa SPEARpesticides metric ndi ΣTUFipronils [log10(X + 1) conversion] Associated.Kuti mumve zambiri za SPEARpesticides metrics komanso kusanthula deta, chonde onani Supplementary Materials.
Mlozera wamtundu wamadzi umasinthasintha mumayendedwe aliwonse a mesoscopic ndi nthawi yonse yoyesera ya mesoscopic.Kutentha kwapakati, pH ndi conductivity zinali 13.1 ° C (± 0.27 ° C), 7.8 (± 0.12) ndi 54.1 (± 2.1) μS / cm (35), motero.Mlingo wa organic carbon woyezedwa m'madzi aukhondo amtsinje ndi 3.1 mg/L.M'mawonedwe a maso a mtsinje kumene chojambulira cha MiniDOT chimayikidwa, mpweya wosungunuka uli pafupi ndi machulukitsidwe (avareji> 8.0 mg/L), kusonyeza kuti mtsinjewo wazungulira.
Kuwongolera kwaubwino komanso kutsimikizika kwamtundu wa fipronil kumaperekedwa pakutulutsidwa kwa data (35).Mwachidule, kuchira kwa ma spikes a laboratory matrix ndi zitsanzo za mesoscopic nthawi zambiri zimakhala m'magulu ovomerezeka (kuchira kwa 70% mpaka 130%), miyezo ya IDL imatsimikizira kuchuluka kwa njira, ndipo zosoweka za labotale ndi zida nthawi zambiri zimakhala zoyera. izi zafotokozedwa m'nkhani yowonjezera..
Chifukwa cha kapangidwe kake, kuchuluka kwa fipronil komwe kumayezedwa nthawi zambiri kumakhala kotsika kuposa mtengo womwe mukufuna (Chithunzi S2) (chifukwa zimatengera masiku 4 mpaka 10 kuti zifike pokhazikika pansi pamikhalidwe yabwino) (30).Poyerekeza ndi mankhwala ena a fipronil, kuchuluka kwa desulfinyl ndi amide kumasintha pang'ono pakapita nthawi, ndipo kusinthasintha kwa ndende mkati mwa mankhwalawa ndi kochepa kusiyana ndi kusiyana pakati pa mankhwala kupatulapo mankhwala otsika kwambiri a sulfone ndi sulfide.Kuchuluka kwa nthawi yoyezera kuyesedwa kwa gulu lililonse lachipatala ndi motere: Fipronil, IDL mpaka 9.07μg/L;Desulfinyl, IDL mpaka 2.15μg/L;Amide, IDL mpaka 4.17μg/L;Sulfidi, IDL Kufikira 0.57μg/lita;ndi sulfone, IDL ndi 1.13μg/lita (35).M'mitsinje ina, mankhwala osakhala a chandamale a fipronil adapezeka, ndiko kuti, mankhwala omwe sanalowe mu mankhwala enaake, koma amadziwika kuti ndi zinthu zowonongeka za mankhwala.Ma mesoscopic membranes omwe amathandizidwa ndi fipronil ya makolo amakhala ndi kuchuluka kwazinthu zowononga zomwe sizinali chandamale zomwe zapezeka (popanda kugwiritsidwa ntchito ngati mankhwala, ndi sulfinyl, amide, sulfide ndi sulfone);izi zikhoza kukhala chifukwa cha kupanga Zowonongeka Zowonongeka ndi / kapena zowonongeka zomwe zimachitika panthawi yosungira katundu ndi (kapena) mu kuyesa kwa mesoscopic kusiyana ndi zotsatira za kuipitsidwa.Palibe mayendedwe owonongeka omwe adawonedwa muzamankhwala a fipronil.Mankhwala osokoneza bongo omwe sali ndi zolinga amapezeka kawirikawiri m'thupi ndi chithandizo chamankhwala, koma chiwerengerocho chimakhala chochepa kusiyana ndi kuchuluka kwa mankhwala omwe sali okonzekera (onani gawo lotsatira la ndondomekoyi).Chifukwa chake, popeza mankhwala owonongeka omwe sali chandamale nthawi zambiri sapezeka pamankhwala otsika kwambiri a fipronil, komanso chifukwa ndende yomwe yadziwika imakhala yocheperako poyerekeza ndi momwe zimachitikira pamankhwala apamwamba kwambiri, zimatsimikiziridwa kuti mankhwalawa omwe sali chandamale amakhala ndi zotsatira zochepa pakuwunika.
Poyesera zofalitsa, benthic macroinvertebrates anali okhudzidwa ndi fipronil, desulfinyl, sulfone, ndi sulfide [Table S1;zambiri zochulukirapo zimaperekedwa motsagana ndi mtundu wa data (35)].Fipronil amide ndi ya ntchentche ya Rhithrogena sp yokha.Poizoni (zakupha), EC50 yake ndi 2.05μg/L [±10.8(SE)].Ma curve-mayankho a mlingo wa 15 wapadera wa msonkho adapangidwa.Misonkho iyi inawonetsa kufa mkati mwa ndende zoyesedwa zoyesedwa (Table S1), ndi taxa yolunjika (monga ntchentche) (Chithunzi S3) ndi taxa wolemera (Chithunzi 1) Njira yokhotakhota ya mlingo idapangidwa.The ndende (EC50) wa fipronil, desulfinyl, sulfone ndi sulfide pa wapadera taxa wa tcheru kwambiri taxa osiyanasiyana kuchokera 0.005-0.364, 0.002-0.252, 0.002-0.061 ndi 0.005-0.043μg/L, motero.Rhithrogena sp.Ndi Sweltsa sp.;Chithunzi S4) ndi otsika kuposa taxa yolekerera (monga Micropsectra / Tanytarsus ndi Lepidostoma sp.) (Table S1).Malinga ndi pafupifupi EC50 pagulu lililonse mu Table S1, ma sulfone ndi ma sulfide ndi omwe amagwira ntchito kwambiri, pomwe ma invertebrates nthawi zambiri sakhudzidwa kwambiri ndi desulfinyl (kupatula ma amide).Miyezo ya momwe chilengedwe chonse chilili, monga kulemera kwa taxa, kuchuluka kwathunthu, pentaploid yonse ndi ntchentche zamwala zonse, kuphatikiza taxa ndi kuchuluka kwa msonkho wina, izi ndizosowa kwambiri mu meso ndipo sizingawerengedwe Jambulani njira yoyankhira mlingo wosiyana.Chifukwa chake, zisonyezo zachilengedwe izi zikuphatikiza mayankho amisonkho omwe sanaphatikizidwe mu SSD.
Kulemera kwa Taxa (mphutsi) yokhala ndi magawo atatu a (A) fipronil, (B) desulfinyl, (C) sulfone, ndi (D) sulfide concentration.Dongosolo lililonse la data limayimira mphutsi kuchokera pamtsinje umodzi kumapeto kwa kuyesa kwa masiku 30.Kulemera kwa misonkho ndi chiwerengero cha msonkho wapadera mumtsinje uliwonse.Kuchuluka kwa mtsinjewu ndi kuchuluka kwanthawi yolemedwa kwa mtsinje uliwonse womwe umayesedwa kumapeto kwa kuyesa kwa masiku 30.Fipronil amide (osasonyezedwa) alibe ubale ndi taxa wolemera.Chonde dziwani kuti x-axis ili pamlingo wa logarithmic.EC20 ndi EC50 yokhala ndi SE ikufotokozedwa mu Table S1.
Pakuchulukirachulukira kwamitundu yonse isanu ya fipronil, kuchuluka kwa Uetridae kudatsika.Kuchuluka kwa kumera (EC50) kwa sulfide, sulfone, fipronil, amide ndi desulfinyl kunawonedwa kutsika ndi 50% pamagulu a 0.03, 0.06, 0.11, 0.78 ndi 0.97μg/L motsatira (Chithunzi 2 ndi Chithunzi S5)M'mayesero ambiri a masiku a 30, mankhwala onse a fipronil, desulfinyl, sulfone ndi sulfide anachedwa, kupatulapo mankhwala otsika kwambiri (Chithunzi 2), ndipo maonekedwe awo anali oletsedwa.Mu chithandizo cha amide, madzi otsekemera omwe anasonkhanitsidwa panthawi yonse yoyesera anali apamwamba kuposa olamulira, ndi chiwerengero cha 0.286μg / lita.Kuphatikizika kwakukulu (4.164μg / lita) panthawi yonse yoyesera kunalepheretsa kutayira, ndipo mlingo wamadzimadzi wa mankhwala apakatikati unali wofanana ndi wa gulu lolamulira.(chithunzi 2).
Kuchulukirachulukira ndi kuchuluka kwa tsiku ndi tsiku komwe kumatuluka pamankhwala aliwonse opanda (A) fipronil, (B) desulfinyl, (C) sulfone, (D) sulfide ndi (E) amide mumayendedwe owongolera Pafupifupi tsiku lililonse amatuluka nembanemba.Kupatulapo kulamulira (n = 6), n = 1. Mtengo wokhazikika ndi nthawi yolemedwa ndi chiwerengero chazomwe zimawonedwa pakuyenda kulikonse.
Mzere wokhotakhota wa mlingo umasonyeza kuti, kuwonjezera pa kuwonongeka kwa taxonomic, kusintha kwapangidwe pamagulu a anthu.Makamaka, mkati mwa mayeso oyeserera, kuchuluka kwa may (Chithunzi S3) ndi kuchuluka kwa taxa (Chithunzi 1) kunawonetsa maubale okhudzana ndi mlingo ndi fipronil, desulfinyl, sulfone, ndi sulfide.Chifukwa chake, tidasanthula momwe kusintha kwamapangidwe uku kumabweretsa kusintha kwa magwiridwe antchito ammudzi poyesa kuchepa kwa zakudya.Kuwonetsa zamoyo zam'madzi zam'madzi ku fipronil, desulfinyl, sulfide ndi sulfone zimakhudza mwachindunji pa biomass ya scraper (Chithunzi 3).Pofuna kuthana ndi zotsatira zoipa za fipronil pa biomass ya scraper, scraper inakhudzanso chlorophyll biomass (Chithunzi 3).Zotsatira za ma coefficients oyipawa ndi kuchuluka kwa chlorophyll a pomwe kuchuluka kwa fipronil ndi degradants kumawonjezeka.Njira zotsatizanazi zikuwonetsa kuti kuwonongeka kwa fipronil kapena fipronil kumabweretsa kuwonjezeka kwa gawo la chlorophyll a (Chithunzi 3).Zimaganiziridwa pasadakhale kuti zotsatira zachindunji pakati pa ndende ya fipronil kapena kuwonongeka ndi chlorophyll biomass ndi ziro, chifukwa ma fipronil ndi mankhwala ophera tizilombo ndipo amakhala ndi kawopsedwe kakang'ono ku algae (mwachitsanzo, EPA pachimake non-vascular plant ndende ndi 100μg / L. fipronil, gulu la disulfoxide, sulfone ndi sulfide; https://epa.gov/pesticide-science-and-assessing-pesticide-risk/aquatic-life-benchmarks-and-ecological-risk), Zotsatira zonse (zitsanzo zovomerezeka) zimathandizira izi malingaliro.
Fipronil ikhoza kuchepetsa kwambiri biomass (zotsatira mwachindunji) za msipu (gulu la scraper ndi mphutsi), koma silimakhudza mwachindunji biomass ya chlorophyll a.Komabe, mphamvu yosalunjika ya fipronil ndi kuonjezera biomass ya chlorophyll a poyankha kuchepa kwa msipu.Mivi ikuwonetsa njira yofananira, ndipo chizindikiro chochotsera (-) chikuwonetsa komwe kumayendera.* Imasonyeza mlingo wa kufunika.
Ma SSD atatu (wosanjikiza wapakatikati okha, wosanjikiza wapakati kuphatikiza data ya ECOTOX, ndi wosanjikiza wapakati kuphatikiza ndi data ya ECOTOX yokonzedwa chifukwa cha kusiyana kwa nthawi yowonekera) adatulutsa ma HC5 mosiyanasiyana (Table S3), koma zotsatira zake zinali mkati mwa SE.M'kafukufuku wotsalayu, tiyang'ana kwambiri pa data ya SSD yokhala ndi maso chilengedwe chonse komanso mtengo wofananira wa HC5.Kuti mumve zambiri pakuwunika kutatu kwa SSD uku, chonde onani zida zowonjezera (Matebulo S2 mpaka S5 ndi Zithunzi S6 ndi S7).Kugawidwa koyenera kwambiri kwa deta (zotsika kwambiri za Akaike chidziwitso chodziwika bwino) chamagulu anayi a fipronil (Chithunzi 4) omwe amagwiritsidwa ntchito pamapu a meso-solid SSD ndi log-gumbel ya fipronil ndi sulfone, ndi weibull wa sulfide And desulfurized γ ( Chithunzi S3).Makhalidwe a HC5 omwe amapezedwa pagulu lililonse amafotokozedwa mu Chithunzi 4 cha chilengedwe cha meso chokha, ndipo mu Table S3 misinkhu ya HC5 kuchokera ku ma data onse atatu a SSD amanenedwa.Makhalidwe a HC50 a fipronil, sulfide, sulfone ndi magulu a desulfinyl [22.1 ± 8.78 ng/L (95% CI, 11.4 mpaka 46.2), 16.9±3.38 ng/L (95% CI, 11.2 mpaka 28.0 ± 8.0), 8 2.66 ng/L (95% CI, 5.44 mpaka 15.8) ndi 83.4±32.9 ng/L (95% CI, 36.4 mpaka 163)] Mankhwalawa ndi otsika kwambiri kuposa kulemera kwa EC50 taxa (chiwerengero chonse cha taxa yapadera) (Table S1 ; zolemba mu tebulo lazinthu zowonjezera ndi ma micrograms pa lita imodzi).
Mu kuyesa kwa meso-scale, pamene akumana ndi (A) fipronil, (B) dessulfinyl fipronil, (C) fipronil sulfone, (D) fipronil sulfide kwa masiku 30, kukhudzidwa kwa mitundu kumafotokozedwa Ndi mtengo wa EC50 wa taxon.Mzere wa buluu umayimira 95% CI.Mzere wopingasa wodutsa umayimira HC5.Mtengo wa HC5 (ng / L) wa pawiri uliwonse uli motere: Fipronil, 4.56 ng / L (95% CI, 2.59 mpaka 10.2);Sulfidi, 3.52 ng/L (1.36 mpaka 9.20);Sulfone, 2.86 ng/ Lita (1.93 mpaka 5.29);ndi sulfinyl, 3.55 ng/lita (0.35 mpaka 28.4).Chonde dziwani kuti x-axis ili pamlingo wa logarithmic.
M'maphunziro asanu am'madera, Fipronil (makolo) adapezeka mu 22% mwa magawo 444 a zitsanzo zam'munda (Table 1).Mafupipafupi odziwika a florfenib, sulfone ndi amide ndi ofanana (18% mpaka 22% ya chitsanzo), maulendo odziwika a sulfide ndi desulfinyl ndi otsika (11% mpaka 13%), pamene zotsalira zowonongeka ndizokwera kwambiri.Ochepa (1% kapena kuchepera) kapena sanazindikire (Table 1)..Fipronil imapezeka kawirikawiri kum'mwera chakum'mawa (52% ya malo) ndipo kawirikawiri kumpoto chakumadzulo (9% ya malo), zomwe zimasonyeza kusiyana kwa ntchito ya benzopyrazole ndi chiopsezo cha mitsinje m'dziko lonselo.Zowononga nthawi zambiri zimawonetsa madera ofanana, okhala ndi ma frequency apamwamba kwambiri kumwera chakum'mawa komanso otsika kwambiri kumpoto chakumadzulo kapena m'mphepete mwa nyanja California.Kuchuluka kwa fipronil kunali kwakukulu kwambiri, kutsatiridwa ndi kholo limodzi la fipronil (90% peresenti ya 10.8 ndi 6.3 ng/L, motsatira) (Table 1) (35).Kuchuluka kwa fipronil (61.4 ng / L), disulfinyl (10.6 ng / L) ndi sulfide (8.0 ng / L) kunatsimikiziridwa kumwera chakum'mawa (m'masabata anayi omaliza a chitsanzo).Kuchuluka kwa sulfone kunadziwika kumadzulo.(15.7 ng/L), amide (42.7 ng/L), dessulfinyl flupirnamide (14 ng/L) ndi fipronil sulfonate (8.1 ng/L) (35).Florfenide sulfone ndiye mankhwala okhawo omwe adawonedwa kuti amapitilira HC5 (Table 1).Pafupifupi ΣTUFipronils pakati pa zigawo zosiyanasiyana zimasiyana kwambiri (Table 1).Pafupifupi dziko lonse ΣTUFipronils ndi 0.62 (malo onse, zigawo zonse), ndipo malo a 71 (16%) ali ndi ΣTUFipronils> 1, zomwe zimasonyeza kuti zingakhale poizoni kwa benthic macroinvertebrates.M'madera anayi mwa asanu omwe amaphunzira (kupatula ku Midwest), pali mgwirizano waukulu pakati pa SPEARpesticides ndi ΣTUFipronil, ndi R2 yosinthidwa kuyambira 0.07 m'mphepete mwa nyanja ya California mpaka 0.34 kum'mwera chakum'mawa (Chithunzi 5).
* Zophatikiza zomwe zimagwiritsidwa ntchito poyesa masoscopic.† ΣTUFipronils, wapakatikati wa kuchuluka kwa mayunitsi a poizoni [anawona kuchuluka kwa magawo anayi a fipronil / ndende yowopsa ya pawiri iliyonse kuchokera ku gawo lachisanu la mitundu yomwe ili ndi kachilombo ka SSD (Chithunzi 4)] Kwa zitsanzo za sabata za fipronil, 4 yomaliza masabata a zitsanzo za mankhwala ophera tizilombo omwe anasonkhanitsidwa pamalo aliwonse anawerengedwa.‡ Chiwerengero cha malo omwe amayezera mankhwala ophera tizilombo.§Chiwerengero cha 90th percentile chimatengera kuchuluka kwa anthu omwe awonedwa pamalopo m'masabata anayi omaliza a kuyesa kwa mankhwala ophera tizilombo.ndi kuchuluka kwa zitsanzo zoyesedwa.¶ Gwiritsani ntchito 95% CI ya mtengo wa HC5 (Chithunzi 4 ndi Table S3, meso okha) kuti muwerenge CI.Dechloroflupinib yawunikidwa m'madera onse ndipo sinapezekepo.ND, sichinazindikiridwe.
Fipronil toxic unit ndi mulingo wa fipronil woyezedwa womwe umagawidwa ndi mtengo wa HC5, womwe umatsimikiziridwa ndi SSD yopezedwa kuchokera pakuyesa kwa media (onani Chithunzi 4).Mzere wakuda, generalized additive model (GAM).Mzere wofiyira wofiyira uli ndi CI ya 95% ya GAM.ΣTUFipronils imasinthidwa kukhala log10 (ΣTUFipronils+1).
Zotsatira zoyipa za fipronil pazamoyo zam'madzi zomwe sizikutsata zalembedwa bwino (15, 21, 24, 25, 32, 33), koma iyi ndi phunziro loyamba lomwe limakhudzidwa ndi malo oyendetsedwa ndi labotale.Madera a taxa adawonetsedwa ndi mankhwala a fipronil, ndipo zotsatira zake zidatulutsidwa pamlingo wa kontinenti.Zotsatira za kuyesa kwa masiku 30 kwa mesocosmic kumatha kutulutsa magulu 15 a tizilombo tating'onoting'ono ta m'madzi (Table S1) osawerengeka m'mabuku, pomwe tizilombo ta m'madzi zomwe zili m'malo osungiramo poizoni zimayimiriridwa (53, 54).Mapiritsi amisonkho okhudzana ndi misonkho (monga EC50) amawonekera pakusintha kwamagulu (monga kuchuluka kwa msonkho komanso kutayika kwachulukidwe) ndi kusintha kwa magwiridwe antchito (monga kutsika kwa zakudya ndi kusintha kwa mawonekedwe).Zotsatira za chilengedwe cha mesoscopic zidatulutsidwa kumunda.M'madera anayi mwa asanu ofufuza ku United States, chiwerengero cha fipronil choyezera m'munda chinali chogwirizana ndi kuchepa kwa chilengedwe cha m'madzi m'madzi oyenda.
Mtengo wa HC5 wa 95% wa zamoyo zomwe zili mumpikisano wapakatikati zimakhala ndi chitetezo, zomwe zikuwonetsa kuti madera onse am'madzi am'madzi amakhudzidwa kwambiri ndi mankhwala a fipronil kuposa momwe amamvekera kale.Mtengo wa HC5 wopezedwa (florfenib, 4.56 ng/lita; desulfoxirane, 3.55 ng/lita; sulfone, 2.86 ng/lita; sulfide, 3.52 ng/lita) ndi kangapo (florfenib) mpaka katatu Kuposa dongosolo la magnitude (desulfinyl) ) pansi pa chiwerengero cha EPA chosachiritsika chamakono [fipronil, 11 ng/lita;desulfinyl, 10,310 ng/lita;sulfone, 37 ng/lita;ndi sulfide, kwa 110 ng/lita (8)].Mayesero a Mesoscopic adazindikira magulu ambiri omwe amakhudzidwa ndi fipronil m'malo mwa omwe amasonyezedwa ndi EPA invertebrate benchmark (magulu a 4 omwe amakhudzidwa kwambiri ndi fipronil, 13 pairs of desulfinyl, 11 sulfone ndi 13 pairs) Sulfide sensitivity) (Chithunzi 4 ndi tebulo) S1).Izi zikuwonetsa kuti zizindikiro sizingateteze mitundu ingapo yomwe imawonedwanso kumayiko apakati, yomwe ilinso yofala m'zamoyo zam'madzi.Kusiyana pakati pa zotsatira zathu ndi zizindikiro zomwe zilipo panopa makamaka chifukwa cha kusowa kwa deta yoyesera ya poizoni ya fipronil yomwe ikugwiritsidwa ntchito pamagulu osiyanasiyana a tizilombo tating'onoting'ono ta m'madzi, makamaka pamene nthawi yowonekera ikupitirira masiku 4 ndipo fipronil imawononga.Pakuyesa kwa masiku a 30 kwa mesocosmic, tizilombo tambiri m'magulu amtundu wa invertebrates timamva kwambiri fipronil kuposa ma Aztec (crustacean), ngakhale atawongolera Aztec The EC50 ya Teike imapangitsanso chimodzimodzi pambuyo pa kusintha kwakukulu.(Kawirikawiri maola a 96) mpaka nthawi yowonongeka (Chithunzi S7).Kugwirizana kwabwinoko kudafikiridwa pakati pa kuyesa kwa membrane wapakatikati ndi kafukufuku yemwe adanenedwa mu ECOTOX pogwiritsa ntchito chamoyo choyesa Chironomus dilutus (tizilombo).N’zosadabwitsa kuti tizilombo ta m’madzi timakhudzidwa kwambiri ndi mankhwala ophera tizilombo.Popanda kusintha nthawi yowonetsera, kuyesa kwa meso-scale ndi deta yokwanira ya nkhokwe ya ECOTOX inasonyeza kuti taxa yambiri idawonedwa kuti imakhala yokhudzidwa kwambiri ndi mankhwala a fipronil kusiyana ndi Clostridium wochepetsedwa (Chithunzi S6).Komabe, posintha nthawi yowonekera, Dilution Clostridium ndi chamoyo chodziwika kwambiri kwa fipronil (kholo) ndi sulfide, ngakhale sichimakhudzidwa ndi sulfone (Chithunzi S7).Zotsatirazi zikuwonetsa kufunikira kophatikiza mitundu ingapo ya zamoyo zam'madzi (kuphatikiza tizilombo tambiri) kuti tipange mankhwala ophera tizilombo omwe angateteze zamoyo zam'madzi.
Njira ya SSD imatha kuteteza msonkho wosowa kapena wosakhudzidwa womwe EC50 yake singadziwike, monga Cinygmula sp., Isoperla fulva ndi Brachycentrus americanus.Miyezo ya EC50 ya kuchuluka kwa taxa ndipo imatha kuwuluka mochulukira kuwonetsa kusintha kwamagulu ammudzi imagwirizana ndi ma HC50 a SSD a fipronil, sulfone ndi sulfide.Ndondomekoyi imathandizira malingaliro otsatirawa: Njira ya SSD yomwe imagwiritsidwa ntchito popanga malire imatha kuteteza anthu onse ammudzi, kuphatikizapo msonkho wosowa kapena wosakhudzidwa ndi anthu ammudzi.Mphepete mwa zamoyo zam'madzi zomwe zimatsimikiziridwa kuchokera ku ma SSD potengera msonkho wochepa chabe kapena msonkho wosamva bwino zitha kukhala zosakwanira pakuteteza zachilengedwe zam'madzi.Izi ndizochitika za desulfinyl (Chithunzi S6B).Chifukwa cha kusowa kwa deta mu nkhokwe ya ECOTOX, EPA yosachiritsika ya invertebrate maziko ndi 10,310 ng / L, yomwe ndi maulamuliro anayi apamwamba kuposa 3.55 ng / L ya HC5.Zotsatira zamitundu yosiyanasiyana yamayankho a taxon opangidwa muzoyeserera za mesoscopic.Kusowa kwa data yapoizoni kumakhala kovuta kwambiri pazinthu zowonongeka (Chithunzi S6), zomwe zingafotokoze chifukwa chake zizindikiro zomwe zilipo zam'madzi za sulfone ndi sulfide zimakhala pafupifupi 15 mpaka 30 zosakhudzidwa kwambiri kuposa mtengo wa SSD HC5 zochokera ku China Universe.Ubwino wa njira yapakatikati ya membrane ndikuti ma EC50 angapo amatha kuzindikirika pakuyesa kamodzi, komwe ndi kokwanira kupanga SSD yathunthu (mwachitsanzo, desulfinyl; Chithunzi 4B ndi Zithunzi S6B ndi S7B), ndipo zimakhudza kwambiri. pa msonkho wachilengedwe wa chilengedwe chotetezedwa Mayankho ambiri.
Kuyesa kwa Mesoscopic kukuwonetsa kuti fipronil ndi zinthu zake zowononga zitha kukhala ndi zotsatira zoyipa kwambiri komanso zosalunjika pa ntchito ya anthu.Mu kuyesa kwa mesoscopic, mankhwala onse asanu a fipronil adawoneka kuti akukhudza kutuluka kwa tizilombo.Zotsatira za kufananitsa pakati pa zochepetsetsa kwambiri komanso zotsika kwambiri (kulepheretsa ndi kulimbikitsa kutulukira kwa munthu kapena kusintha kwa nthawi yotuluka) zimagwirizana ndi zotsatira zomwe zanenedwa kale za kuyesa kwa meso pogwiritsa ntchito insecticide bifenthrin (29).Kuwonekera kwa akuluakulu kumapereka ntchito zofunikira zachilengedwe ndipo zimatha kusinthidwa ndi zowononga monga fipronil (55, 56).Kutuluka nthawi imodzi sikofunikira pakubala tizilombo komanso kulimbikira kwa anthu, komanso kuti pakhale tizilombo tokhwima, zomwe zitha kugwiritsidwa ntchito ngati chakudya cha nyama zam'madzi ndi zapadziko lapansi (56).Kuletsa kumera kwa mbande kumatha kusokoneza kusinthana kwazakudya pakati pa zamoyo zam'madzi ndi zamoyo zam'mphepete mwa nyanja, ndikufalitsa zowononga zam'madzi m'zachilengedwe zapadziko lapansi (55, 56).Kuchepa kwa kuchuluka kwa scrapers (tizilombo zodya ndere) zomwe zidawonedwa mu kuyesa kwa meso-scale kudachepetsa kumwa ndere, zomwe zidapangitsa kuti chlorophyll achuluke (Chithunzi 3).Kuphulika kwa trophic kumeneku kumasintha kutulutsa kwa kaboni ndi nayitrogeni muzakudya zamadzimadzi, mofanana ndi kafukufuku yemwe amawunika zotsatira za pyrethroid bifenthrin pamagulu a benthic (29).Choncho, phenylpyrazoles, monga fipronil ndi zowonongeka zake, pyrethroids, ndipo mwina mitundu ina ya mankhwala ophera tizilombo, akhoza kulimbikitsa mwachindunji kuwonjezeka kwa algal biomass ndi kusokoneza mpweya ndi nayitrogeni m'mitsinje yaing'ono.Zotsatira zina zitha kupitilira ku kuwonongeka kwa mayendedwe a carbon ndi nayitrogeni pakati pa zamoyo zam'madzi ndi zapadziko lapansi.
Zambiri zomwe zidapezeka pamayeso apakati pa membrane zidatilola kuwunika momwe chilengedwe chimakhalira ndi kuchuluka kwa fipronil komwe kumayesedwa m'maphunziro akulu akulu omwe adachitika m'magawo asanu a United States.M'mitsinje yaying'ono ya 444, 17% ya kuchuluka kwa mankhwala amodzi kapena angapo a fipronil (avereji pa masabata a 4) adaposa mtengo wa HC5 wopezedwa kuchokera ku mayeso atolankhani.Gwiritsani ntchito SSD kuchokera pa kuyesa kwa meso-scale kuti mutembenuzire ndende ya fipronil pawiri kukhala index yokhudzana ndi kawopsedwe, ndiko kuti, kuchuluka kwa mayunitsi a kawopsedwe (ΣTUFipronils).Mtengo wa 1 ukuwonetsa kawopsedwe kapena kuchulukira kwa fipronil kupitilira chitetezo chodziwika Mitundu yamtengo 95%.Ubale wofunikira pakati pa ΣTUFipronil m'zigawo zinayi mwa zisanu ndi chizindikiro cha SPEARpesticides cha thanzi la anthu opanda vertebrate amasonyeza kuti fipronil ikhoza kusokoneza midzi ya benthic invertebrate m'mitsinje m'madera angapo a United States.Zotsatira izi zimathandizira lingaliro la Wolfram et al.(3) Chiwopsezo cha phenpyrazole mankhwala ophera tizilombo kumadzi padziko lapansi ku United States sichimveka bwino chifukwa zotsatira za tizilombo ta m'madzi zimachitika m'munsi mwa malire apano.
Mitsinje yambiri yokhala ndi ma fipronil pamwamba pa mlingo wapoizoni imapezeka m'chigawo chakum'mwera chakum'mawa komwe kuli ndi matauni ambiri (https://webapps.usgs.gov/rsqa/#!/region/SESQA).Kuwunika koyambirira kwa derali sikunangotsimikizira kuti fipronil ndiye vuto lalikulu lomwe limakhudza dongosolo la anthu osagwirizana ndi mtsinje mumtsinje, komanso kuti mpweya wosungunuka wochepa, zakudya zowonjezera, kusintha kwa kayendedwe kake, kuwonongeka kwa malo, ndi mankhwala ena ophera tizilombo komanso Gulu loipitsa ndilofunika kwambiri. gwero la nkhawa (57).Kusakanizika kwa zodetsa nkhawa kumeneku kumagwirizana ndi "urban river syndrome", komwe ndi kuwonongeka kwa chilengedwe cha mitsinje komwe kumawonedwa kawirikawiri ndikugwiritsa ntchito malo akumatauni (58, 59).Zizindikiro zogwiritsira ntchito nthaka m’matauni m’chigawo cha Kum’mwera chakum’mawa zikukula ndipo zikuyembekezeka kukwera pamene chiwerengero cha anthu chikukula.Zotsatira za chitukuko cha m'matauni ndi mankhwala ophera tizilombo pamadzi osefukira akuyembekezeka kuwonjezeka (4).Ngati kutukuka kwa mizinda komanso kugwiritsa ntchito fipronil kukupitilira kukula, kugwiritsa ntchito mankhwala ophera tizilombo m'mizinda kumatha kukhudza kwambiri madera ozungulira.Ngakhale kuwunika kwa meta kumatsimikizira kuti kugwiritsa ntchito mankhwala ophera tizilombo kumawopseza zachilengedwe zapadziko lonse lapansi (2, 60), tikuganiza kuti kuwunikaku kumachepetsa kukhudzidwa kwapadziko lonse kwa mankhwala ophera tizilombo posapatula kugwiritsidwa ntchito kumatauni.
Zovuta zosiyanasiyana, kuphatikiza mankhwala ophera tizilombo, zimatha kukhudza madera amtundu wa macroinvertebrate m'malo otukuka (matauni, ulimi ndi kugwiritsa ntchito malo osakanikirana) ndipo zitha kukhala zokhudzana ndi kugwiritsa ntchito nthaka (58, 59, 61).Ngakhale kafukufukuyu adagwiritsa ntchito chizindikiro cha SPEARpesticides komanso mawonekedwe amadzi am'madzi okhudzana ndi kawopsedwe ka fipronil kuti achepetse kukhudzidwa kwa zinthu zomwe zimasokoneza, magwiridwe antchito a chizindikiro cha SPEARpesticides angakhudzidwe ndi kuwonongeka kwa malo, ndipo fipronil imatha kufananizidwa ndi mankhwala ena ophera tizilombo (4, 17), 51 ndime 57).Komabe, njira yovutitsa kambirimbiri idapangidwa pogwiritsa ntchito miyeso yam'munda kuchokera kumaphunziro awiri oyamba amchigawo (Midwestern ndi Kumwera chakum'mawa) adawonetsa kuti mankhwala ophera tizilombo ndi ofunikira kumtunda kwa mitsinje ya macroinvertebrate m'mitsinje yoyenda.M'mitundu iyi, zofotokozera zofunikira zimaphatikizira mankhwala ophera tizilombo (makamaka bifenthrin), zakudya ndi malo okhala m'mitsinje yambiri yaulimi ku Midwest, ndi mankhwala ophera tizilombo (makamaka fipronil) m'mizinda yambiri kumwera chakum'mawa.Kusintha kwa mpweya, zakudya ndi kuyenda (61, 62).Choncho, ngakhale kuti maphunziro a m'madera akuyesa kuthana ndi zotsatira za kupsinjika kwa mankhwala osagwiritsa ntchito mankhwala pa zizindikiro zoyankhira ndikusintha zizindikiro zolosera kuti zifotokoze zotsatira za fipronil, zotsatira za kafukufukuyu zimathandizira maganizo a fipronil.) Iyenera kuonedwa kuti ndi imodzi mwazomwe zimayambitsa kupanikizika kwa mitsinje yaku America, makamaka kum'mwera chakum'mawa kwa United States.
Kuwonongeka kwa mankhwala ophera tizilombo m'chilengedwe sikudziwika kawirikawiri, koma kuopsa kwa zamoyo zam'madzi kungakhale kovulaza kwambiri kuposa thupi la kholo.Pankhani ya fipronil, maphunziro a m'munda ndi kuyesa kwa maso-scale awonetsa kuti zinthu zowonongeka ndizofala monga momwe thupi la makolo limakhalira mumitsinje yotsatiridwa ndipo zimakhala ndi poizoni yemweyo kapena wapamwamba (Table 1).Pakuyesa kwa membrane wapakatikati, fluorobenzonitrile sulfone inali yowopsa kwambiri pamankhwala owononga mankhwala omwe adaphunziridwa, ndipo inali yapoizoni kwambiri kuposa gulu la makolo, ndipo idapezekanso pafupipafupi ngati yapawiri ya kholo.Ngati mankhwala ophera tizilombo amangoyezedwa, zomwe zingachitike ndi kawopsedwe sizingadziwike, ndipo kusowa kwa chidziwitso cha kawopsedwe pakuwonongeka kwa mankhwala kumatanthauza kuti zomwe zimachitika komanso zotsatira zake zitha kunyalanyazidwa.Mwachitsanzo, chifukwa chosowa chidziwitso cha kawopsedwe ka zinthu zowonongeka, kuunika kwathunthu kwa mankhwala ophera tizilombo ku mitsinje ya ku Switzerland kunachitika, kuphatikiza zinthu 134 zowononga mankhwala, ndipo gulu lokhalo la makolo ndilomwe limaganiziridwa kuti ndilo gawo la makolo pakuwunika kwake kwachilengedwe.
Zotsatira zakuwunika kwachiwopsezo kwachilengedweku zikuwonetsa kuti mankhwala a fipronil ali ndi zotsatira zoyipa pa thanzi la mitsinje, chifukwa chake titha kunena momveka bwino kuti zowopsa zimatha kuwonedwa kulikonse komwe mankhwala a fipronil amapitilira mulingo wa HC5.Zotsatira za kuyesa kwa mesoscopic ndizodziyimira pawokha, zomwe zikuwonetsa kuti kuchuluka kwa fipronil ndi zinthu zomwe zimawonongeka mu tax tax zambiri ndizotsika kwambiri kuposa zomwe zidalembedwa kale.Tikukhulupirira kuti zomwe zapezedwazi zitha kufalikira mpaka ku protobiota m'mitsinje yodziwika bwino kulikonse.Zotsatira za kuyesa kwa meso-scale zidagwiritsidwa ntchito pamaphunziro akulu akumunda (mitsinje yaying'ono 444 yopangidwa ndi matawuni, ulimi, ndi malo osakanikirana amitundu yonse ku United States), ndipo zidapezeka kuti kuchuluka kwa mitsinje yambiri. kumene fipronil anapezeka akuyembekezeka kukhala Kuopsa kwake kumasonyeza kuti zotsatirazi zikhoza kufalikira ku mayiko ena kumene fipronil amagwiritsidwa ntchito.Malinga ndi malipoti, chiwerengero cha anthu omwe amagwiritsa ntchito Fipronil chikuwonjezeka ku Japan, UK ndi US (7).Fipronil imapezeka pafupifupi kontinenti iliyonse, kuphatikiza Australia, South America ndi Africa (https://coherentmarketinsights.com/market-insight/fipronil-market-2208).Zotsatira za kafukufuku wa meso-to-field zomwe zafotokozedwa pano zikuwonetsa kuti kugwiritsa ntchito fipronil kungakhale ndi tanthauzo lachilengedwe padziko lonse lapansi.
Kuti mudziwe zambiri za nkhaniyi, chonde onani http://advances.sciencemag.org/cgi/content/full/6/43/eabc1299/DC1
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Funsoli limagwiritsidwa ntchito poyesa ngati ndinu mlendo ndikuletsa kutumiza sipamu zokha.
Janet L. Miller, Travis S. Schmidt, Peter C. Van Metre, Barbara Mahler ( Barbara J. Mahler, Mark W. Sandstrom, Lisa H. Nowell, Daren M. Carlisle, Patrick W. Moran
Kafukufuku wasonyeza kuti mankhwala ophera tizilombo omwe amapezeka kawirikawiri m'mitsinje ya ku America ndi oopsa kwambiri kuposa momwe ankaganizira poyamba.
Janet L. Miller, Travis S. Schmidt, Peter C. Van Metre, Barbara Mahler ( Barbara J. Mahler, Mark W. Sandstrom, Lisa H. Nowell, Daren M. Carlisle, Patrick W. Moran
Kafukufuku wasonyeza kuti mankhwala ophera tizilombo omwe amapezeka kawirikawiri m'mitsinje ya ku America ndi oopsa kwambiri kuposa momwe ankaganizira poyamba.
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