Maganin kashe qwari a cikin rafuka yana ƙara zama abin damuwa a duniya, amma akwai ɗan bayani kan amintaccen yanayin yanayin ruwa.A cikin gwajin mesocosmic na kwanaki 30, ƴan asalin benthic invertebrates na ruwa an fallasa su ga fipronil na kwarin kwari da nau'ikan samfuran lalata iri huɗu.Fipronil fili ya haifar da canje-canje a cikin fitowar da trophic cascade.Mahimmancin maida hankali (EC50) wanda fipronil da sulfide, sulfone da desulfinyl lalata samfuran ke haifar da amsawar 50%.Taxanes ba sa kula da fipronil.Ana amfani da haɗarin haɗari na 5% na nau'in da abin ya shafa daga ƙimar mesocosmic EC50 15 don canza ma'auni na fipronil a cikin samfurin filin zuwa jimlar raka'a masu guba (∑TUFipronils).A cikin 16% na rafukan da aka zana daga nazarin yanki guda biyar, matsakaicin ∑TUFipronil ya wuce 1 (yana nuna guba).Alamun invertebrate na nau'ikan da ke cikin haɗari suna da alaƙa mara kyau tare da TUTUipronil a cikin yankuna huɗu na samfura biyar.Wannan kima na haɗarin muhalli ya nuna cewa ƙananan ƙwayoyin fipronil za su rage al'ummomin rafi a yawancin sassan Amurka.
Duk da cewa samar da sinadarai na roba ya karu sosai a cikin 'yan shekarun nan, tasirin wadannan sinadarai a kan halittun da ba su da manufa ba a fahimta sosai (1).A cikin ruwan saman da kashi 90% na filayen noma na duniya ke ɓacewa, babu bayanai game da magungunan kashe qwari na noma, amma inda aka samu bayanai, lokacin da maganin kashe qwari ya wuce matakin da aka tsara ya kai rabin (2).Wani bincike da aka yi na magungunan kashe qwari na noma a cikin ruwa a cikin Amurka ya gano cewa a cikin kashi 70% na wuraren da ake yin samfur, aƙalla maganin kashe qwari guda ɗaya ya wuce matakin tsari (3).Koyaya, waɗannan ƙididdigar meta-nazari (2, 3) sun fi mayar da hankali ne kawai kan ruwan saman da amfanin ƙasar noma ya shafa, kuma taƙaitaccen nazari ne.Maganin kashe qwari, musamman magungunan kashe qwari, suma suna da yawa a cikin magudanar ruwa a birane (4).Yana da wuya a gudanar da cikakken kimantawa na magungunan kashe qwari a cikin ruwan saman da aka fitar daga aikin gona da yanayin birane;don haka, ba a sani ba ko magungunan kashe qwari na haifar da babbar barazana ga albarkatun ruwa da kuma amincinsu na muhalli.
Benzopyrazoles da neonicotinoids sun kai kashi ɗaya bisa uku na kasuwar maganin kashe qwari ta duniya a cikin 2010 (5).A cikin ruwa mai zurfi a Amurka, fipronil da samfuran lalacewa (phenylpyrazoles) sune magungunan kashe qwari da aka fi sani da su, kuma yawancin su yawanci sun wuce matakan ruwa (6-8).Ko da yake neonicotinoids sun ja hankali saboda tasirin su ga ƙudan zuma da tsuntsaye da kuma yawansu (9), fipronil ya fi guba ga kifi da tsuntsaye (10), yayin da sauran phenylpyrazoles Class mahadi suna da tasirin herbicidal (5).Fipronil wani tsari ne na kashe kwari da ake amfani da shi don magance kwari a cikin birane da wuraren noma.Tun lokacin da fipronil ya shiga kasuwar duniya a cikin 1993, amfani da fipronil a Amurka, Japan da Ingila ya karu sosai (5).A Amurka, ana amfani da fipronil don sarrafa tururuwa da tururuwa, kuma ana amfani da su a cikin amfanin gona da suka hada da masara (ciki har da maganin iri), dankali da gonaki (11, 12).Amfanin noma na fipronil a Amurka ya kai kololuwa a cikin 2002 (13).Kodayake babu bayanan amfani da birane na ƙasa, amfani da birane a California ya kai kololuwa a cikin 2006 da 2015 (https://calpip.cdpr.ca) .gov/main .cfm, shiga Disamba 2, 2019).Kodayake ana samun babban adadin fipronil (6.41μg / L) a cikin rafuka a wasu yankunan noma tare da ƙimar aikace-aikacen (14), idan aka kwatanta da rafukan noma, rafukan birane a cikin Amurka gabaɗaya suna da ƙarin ganowa da haɓaka mafi girma, tabbatacce ga faruwar hadari yana da alaƙa da gwajin (6, 7, 14-17).
Fipronil yana shiga cikin yanayin yanayin ruwa na ruwa ko leaches daga ƙasa zuwa cikin rafi (7, 14, 18).Fipronil yana da ƙarancin rashin ƙarfi (Dokar Henry akai-akai 2.31 × 10-4 Pa m3 mol-1), ƙarancin solubility na ruwa zuwa matsakaici (3.78 mg / l a 20 ° C), da matsakaicin hydrophobicity (log Kow shine 3.9 zuwa 4.1)), motsi a cikin ƙasa yana da ƙanƙanta (log Koc shine 2.6 zuwa 3.1) (12, 19), kuma yana nuna tsayin daka zuwa matsakaici a cikin yanayi (20).Finazepril yana lalacewa ta hanyar photolysis, hadawan abu da iskar shaka, pH-dogara hydrolysis da raguwa, samar da manyan abubuwa guda hudu masu lalata: dessulfoxyphenapril (ko sulfoxide), phenaprenip sulfone (sulfone), Filofenamide (amide) da filofenib sulfide (sulfide).Abubuwan lalatawar Fipronil sun kasance sun fi kwanciyar hankali da dorewa fiye da mahallin mahaifa (21, 22).
Gubar fipronil da lalatarsa ​​zuwa nau'ikan da ba a yi niyya ba (kamar invertebrates na ruwa) an rubuta su da kyau (14, 15).Fipronil wani fili ne na neurotoxic wanda ke yin tsangwama tare da hanyar ion chloride ta hanyar tashar chloride wanda gamma-aminobutyric acid ya tsara a cikin kwari, yana haifar da isasshen maida hankali don haifar da tashin hankali da mutuwa (20).Fipronil yana da zaɓaɓɓen mai guba, don haka yana da kusancin mai karɓar mai karɓa ga kwari fiye da dabbobi masu shayarwa (23).Ayyukan kwari na samfuran lalata fipronil sun bambanta.Rashin guba na sulfone da sulfide zuwa ruwan invertebrates mara kyau yana kama ko mafi girma fiye da na mahallin mahaifa.Desulfinyl yana da matsakaitan guba amma ba shi da guba fiye da mahallin mahaifa.Dan kadan mara guba (23, 24).Lalacewar invertebrates na ruwa zuwa fipronil da lalata fipronil ya bambanta sosai a tsakanin haraji (15), kuma a wasu lokuta ma ya wuce tsari na girma (25).A ƙarshe, akwai shaidar cewa phenylpyrazoles sun fi guba ga tsarin halitta fiye da yadda aka yi tunani a baya (3).
Ma'auni na nazarin halittu na ruwa dangane da gwajin guba na dakin gwaje-gwaje na iya yin la'akari da haɗarin yawan fili (26-28).Yawanci ana kafa ka'idodin ruwa ta hanyar gwajin guba na ɗabi'a guda ɗaya ta amfani da nau'in invertebrate ɗaya ko da yawa (misali, Diptera: Chironomidae: Chironomus da Crustacea: Daphnia magna da Hyalella azteca).Wadannan kwayoyin gwajin suna da sauƙin noma fiye da sauran macroinvertebrates na benthic (misali, phe genus::), kuma a wasu lokuta ba sa kula da gurɓataccen abu.Misali, D. Magna baya kula da karafa da yawa fiye da wasu kwari, yayin da A. zteca baya kula da bifenthrin kwarin pyrethroid fiye da yadda yake ji da tsutsotsi (29, 30).Wani ƙayyadaddun alamomin da ake da su shine ƙarshen ƙarshen da aka yi amfani da su a cikin lissafin.Mahimman ma'auni sun dogara ne akan mace-mace (ko gyarawa don crustaceans), yayin da ma'auni na yau da kullum yawanci suna dogara ne akan ƙarshen ƙarshen (kamar girma da haifuwa) (idan akwai).Duk da haka, akwai tartsatsi da ke yaɗuwa, kamar haɓaka, fitowa, gurɓatacce, da jinkirin ci gaba, wanda zai iya rinjayar nasarar haraji da haɓakar al'umma.Sakamakon haka, ko da yake maƙasudin yana ba da baya ga mahimmancin nazarin halittu na tasirin, dacewar muhalli a matsayin kofa don guba ba shi da tabbas.
Don ƙarin fahimtar tasirin mahadi na fipronil akan yanayin yanayin ruwa na benthic (invertebrates da algae), an kawo al'ummomin benthic na halitta a cikin dakin gwaje-gwaje kuma an fallasa su zuwa matakan maida hankali yayin kwararar kwanaki 30 na Fipronil ko ɗayan gwaje-gwajen lalata fipronil huɗu.Manufar bincike ita ce samar da takamaiman nau'in tasirin sakamako na 50% (darajar EC50) ga kowane fili na fipronil wanda ke wakiltar faffadan haraji na al'ummar kogi, da kuma tantance tasirin gurɓatattun abubuwa akan tsarin al'umma da aiki [watau haɗarin haɗari] 5 % Na nau'in da abin ya shafa (HC5) da kuma tasirin kai tsaye kamar canjin fitowar da yanayin zafi].Sa'an nan kuma an yi amfani da kofa (ƙimar HC5 ta musamman) da aka samu daga gwajin mesoscopic zuwa filin da Cibiyar Nazarin Kasa ta Amurka (USGS) ta tattara daga yankuna biyar na Amurka (Arewa maso Gabas, Kudu maso Gabas, Midwest, Northwest Pacific, da Central California). Yankunan bakin teku) Bayanai) azaman ɓangare na ƙimar ƙimar rafin yanki na USGS (https://webapps.usgs.gov/rsqa/#!/).Kamar yadda muka sani, wannan shine farkon kimanta haɗarin muhalli.Yana yin cikakken bincike game da tasirin mahaɗan fipronil akan ƙwayoyin benthic a cikin mahallin meso-mai sarrafawa, sannan yana amfani da waɗannan sakamakon zuwa kimamin filin nahiya.
An gudanar da gwajin mesocosmic na kwanaki 30 a USGS Aquatic Laboratory (AXL) a Fort Collins, Colorado, Amurka daga Oktoba 18th zuwa Nuwamba 17th, 2017, don ranar 1 na gida da kwanaki 30 na gwaji.An kwatanta hanyar a baya (29, 31) kuma dalla-dalla a cikin ƙarin kayan.Saitin sararin samaniya na meso ya ƙunshi magudanar ruwa guda 36 a cikin magudanan ruwa guda huɗu (tankunan ruwa masu zagayawa).Kowane rafi mai rai yana sanye da na'ura mai sanyaya don kiyaye zafin ruwa kuma ana haskaka shi da zagayowar haske-16:8.Matsakaicin matakin meso shine bakin karfe, wanda ya dace da hydrophobicity na fipronil (log Kow = 4.0) kuma ya dace da abubuwan tsabtace kwayoyin halitta (Figure S1).Ruwan da aka yi amfani da shi don gwajin meso-sikelin an tattara shi daga kogin Cache La Poudre (maɓuɓɓuka masu tasowa ciki har da Rocky Mountain National Park, National Forest and Continental Divide) kuma an adana su a cikin tankunan ajiya na polyethylene guda hudu na AXL.Binciken da aka yi a baya na laka da samfuran ruwa da aka tattara daga wurin ba a sami wani maganin kashe kwari ba (29).
Tsarin gwaji na meso-sikelin ya ƙunshi rafukan sarrafawa guda 30 da rafukan sarrafawa guda 6.Ruwan jiyya yana karɓar ruwan da aka kula da shi, kowannensu ya ƙunshi abubuwan da ba a daidaita su ba na mahadi na fipronil: fipronil (fipronil (Sigma-Aldrich, CAS 120068-37-3), amide (Sigma-Aldrich, CAS 205650-69-7), ƙungiyar desulfurization. [Hukumar Kare Muhalli ta Amurka (EPA) Laburaren Kwari, CAS 205650-65-3], sulfone (Sigma-Aldrich, CAS 120068-37-2) da sulfide (Sigma-Aldrich, CAS 120067-83-6); duk tsafta ≥ 97.8% bisa ga ƙimar amsa da aka buga (7, 15, 16, 18, 21, 23, 25, 32, 33). Tare da deionized ruwa zuwa ƙarar da ake buƙata don shirya wani bayani mai mahimmanci, saboda adadin methanol a cikin kashi ya bambanta, ya zama dole a ƙara methanol zuwa duk rafukan magani kamar yadda ake buƙata. 0.05 ml/L) a cikin rafukan.Tsakiyar kallon sauran rafukan sarrafawa guda uku sun sami ruwan kogi ba tare da methanol ba, in ba haka ba an bi da su kamar sauran rafukan.
A ranar 8th, ranar 16th da ranar 26th, ana auna yawan zafin jiki, ƙimar pH, ƙarfin lantarki da lalatawar fipronil da fipronil a cikin membrane mai gudana.Don yin la'akari da lalacewar mahaifa fipronil a lokacin gwajin watsa labaru, an yi amfani da fipronil (iyaye) don kula da mucosa na hanji na ruwa na tsawon kwanaki uku [kwanakin 5, 12 da 21 (n = 6)] don zafin jiki, pH, Gudanar da aiki, fipronil da samfurin lalatawar fipronil.An tattara samfuran nazarin magungunan kashe qwari ta hanyar tace 10 ml na ruwa mai gudana a cikin gilashin amber 20 ml ta hanyar sirinji Whatman 0.7-μm GF/F sanye da babban allura mai diamita.An daskarar da samfuran nan da nan aka aika zuwa dakin gwaje-gwaje na ingancin ruwa na USGS (NWQL) a Lakewood, Colorado, Amurka don bincike.Yin amfani da ingantacciyar hanyar hanyar da aka buga a baya, Fipronil da samfuran lalata 4 a cikin samfuran ruwa an ƙaddara su ta hanyar allurar ruwa kai tsaye (DAI) ruwa chromatography-tandem mass spectrometry (LC-MS / MS; Agilent 6495).An kiyasta matakin gano kayan aiki (IDL) a matsayin mafi ƙarancin ma'aunin daidaitawa wanda ya dace da ma'aunin tantance ingancin;IDL na fipronil shine 0.005 μg/L, kuma IDL na sauran fipronil huɗu shine 0.001 μg/L.Ƙarin kayan yana ba da cikakken bayanin hanyoyin da ake amfani da su don auna ma'auni na fipronil, ciki har da kula da inganci da hanyoyin tabbatarwa (alal misali, samfurin dawo da, spikes, dubawa na ɓangare na uku, da blanks).
A ƙarshen gwajin Mesocosmic na kwanaki 30, an kammala ƙididdigewa da gano manyan invertebrates na manya da tsutsa (babban wurin tattara bayanai).Ana tattara manya masu tasowa daga gidan yanar gizo kowace rana kuma a daskare su a cikin bututun Falcon centrifuge mai tsabta 15 ml.A ƙarshen gwajin (rana 30), abubuwan da ke cikin membrane a cikin kowane rafi an goge su don cire duk wani invertebrates, kuma sieved (250 μm) kuma an adana shi a cikin 80% ethanol.Timberline Aquatics (Fort Collins, CO) ya kammala tantance harajin larvae da manya invertebrates zuwa mafi ƙasƙanci matakin haraji mai yiwuwa, yawanci nau'in.A ranakun 9, 19 da 29, an auna chlorophyll a cikin ninki uku a cikin mesoscopic membrane na kowane rafi.Dukkan bayanan sinadarai da halittu a matsayin wani ɓangare na gwajin mesoscopic ana bayar da su a cikin sakin bayanan da ke biye (35).
An gudanar da binciken muhalli a cikin ƙananan koguna (wading) a cikin manyan yankuna biyar na Amurka, kuma an kula da magungunan kashe qwari a lokacin bayanan da ya gabata.A takaice dai, bisa la'akari da amfanin gona da filayen birane (36-40), an zaɓi wurare 77 zuwa 100 a kowane yanki (wuri 444 gaba ɗaya).A lokacin bazara da bazara na shekara guda (2013-2017), ana tattara samfuran ruwa sau ɗaya a mako a kowane yanki na makonni 4 zuwa 12.Ƙayyadaddun lokaci ya dogara da yankin da ƙarfin ci gaba.Sai dai tashoshin tashoshi 11 da ke yankin arewa maso gabas kusan suna cikin magudanar ruwa.Babu ci gaba, sai dai samfurin guda ɗaya kawai aka tattara.Tun da lokacin sa ido don magungunan kashe qwari a cikin nazarin yanki ya bambanta, don kwatantawa, kawai samfurori huɗu na ƙarshe da aka tattara a kowane rukunin yanar gizon ana la'akari da su anan.Ana ɗauka cewa samfurin guda ɗaya da aka tattara a yankin arewa maso gabas da ba a haɓaka ba (n = 11) zai iya wakiltar lokacin ɗaukan sati 4.Wannan hanyar tana haifar da adadin adadin abubuwan lura da magungunan kashe qwari (sai dai wurare 11 a Arewa maso Gabas) da tsawon lokacin lura;an yi imani da cewa makonni 4 ya isa tsayin daka don ɗaukar dogon lokaci ga biota, amma gajeriyar isa cewa al'ummomin muhalli ba za su warke daga waɗannan lambobin sadarwa ba.
A cikin yanayin isassun kwararar ruwa, ana tattara samfurin ruwa ta hanyar saurin gudu da tsayin daka da yawa (41).Lokacin da kwararar bai isa ba don amfani da wannan hanya, zaku iya tattara samfurori ta hanyar haɗakarwa mai zurfi na samfurori ko ɗauka daga tsakiyar nauyi na kwarara.Yi amfani da sirinji mai girma da tace diski (0.7μm) don tattara 10 ml na samfurin da aka tace (42).Ta hanyar DAI LC-MS/MS/MS/MS, an yi nazarin samfuran ruwa a NWQL don 225 magungunan kashe qwari da samfuran lalata ƙwayoyin cuta, gami da fipronil da samfuran lalata 7 (dessulfinyl fipronil, fipronil) Sulfides, fipronil sulfone, deschlorofipronil, desthiol, amidepron fipron, desthiol. fipronil da fipronil).).Mafi ƙarancin matakan rahoto don nazarin filin sune: fipronil, desmethylthio fluorobenzonitrile, fipronil sulfide, fipronil sulfone, da deschlorofipronil 0.004 μg/L;dessulfinyl fluorfenamide da kuma ƙaddamar da fipronil amide shine 0.009 μg / lita;Matsakaicin fipronil sulfonate shine 0.096 μg / lita.
An yi samfurin al'ummomin da ba su da invertebrates a ƙarshen kowane yanki (baza/ bazara), yawanci a lokaci ɗaya da taron samfurin maganin kwari na ƙarshe.Bayan lokacin girma da yawan amfani da magungunan kashe qwari, lokacin samfurin ya kamata ya yi daidai da yanayin ƙarancin ruwa, kuma ya kamata ya dace da lokacin da al'ummar kogin invertebrate ke balaga kuma galibi yana cikin matakin rayuwar tsutsa.Yin amfani da samfurin Surber tare da ragar 500μm ko gidan yanar gizo na D-frame, an kammala samfurin al'umma mai invertebrate a cikin 437 daga cikin 444 shafuka.An kwatanta hanyar yin samfur dalla-dalla a cikin ƙarin kayan.A kan NWQL, duk invertebrates yawanci ana gano su kuma an jera su a matakin jinsi ko jinsi.Duk bayanan sinadarai da halittu da aka tattara a wannan filin kuma aka yi amfani da su a cikin wannan rubutun ana iya samun su a cikin sakin bayanan da ke gaba (35).
Don mahaɗan fipronil guda biyar da aka yi amfani da su a cikin gwajin mesoscopic, ƙaddamar da ƙwayar invertebrates na tsutsa ya ragu da 20% ko 50% an ƙididdige su dangane da sarrafawa (watau EC20 da EC50).Bayanan [x = fipronil mai nauyin lokaci mai nauyi (duba ƙarin kayan don cikakkun bayanai), y = yalwar tsutsa ko wasu ma'auni] an daidaita su zuwa fakitin R (43) ta hanyar amfani da hanyar logarithmic regression mai siga uku"dc".Layin ya dace da kowane nau'in (larvae) tare da wadataccen wadataccen abu kuma yana saduwa da wasu ma'auni na sha'awa (misali, wadatar haraji, jimlar mayfly mai yawa, da wadatar duka) don ƙara fahimtar tasirin al'umma.Ana amfani da ƙididdiga na Nash-Sutcliff (45) don kimanta ƙirar ƙirar, inda ƙarancin ƙirar ƙirar zai iya karɓar ƙima mara kyau mara iyaka, kuma ƙimar cikakkiyar dacewa ita ce 1.
Don gano sakamakon abubuwan da ke tattare da fipronil akan fitowar kwari a cikin gwaji, an kimanta bayanan ta hanyoyi biyu.Na farko, ta hanyar rage matsakaita bayyanar meso mai sarrafawa daga bayyanar kowane magani yana gudana meso, tarawar yau da kullun na kwari daga kowane meso mai gudana (jimlar adadin duk mutane) an daidaita su zuwa sarrafawa.Yi ƙirƙira waɗannan dabi'u a kan lokaci don fahimtar karkatar da mai shiga tsakani na jiyya daga mai shiga tsakani a cikin gwajin kwanaki 30.Na biyu, lissafta jimillar adadin abin da ya faru na kowane mesophyll mai gudana, wanda aka bayyana a matsayin rabon adadin mesophylls a cikin da aka ba da shi zuwa matsakaicin adadin larvae da manya a cikin rukunin kulawa, kuma ya dace da koma bayan logarithmic mai ma'ana uku. .Duk kwari da aka tattara sun fito ne daga dangi biyu na dangin Chironomidae, don haka an yi nazarin haɗin gwiwa.
Canje-canje a tsarin al'umma, kamar asarar haraji, ƙila a ƙarshe ya dogara da tasirin abubuwa masu guba kai tsaye da kai tsaye, kuma yana iya haifar da canje-canje a cikin ayyukan al'umma (misali, trophic cascade).Don gwada cascade na trophic, an kimanta hanyar sadarwa mai sauƙi ta hanyar amfani da hanyar bincike ta hanyar (R fakitin "piecewiseSEM") (46).Don gwaje-gwaje na mesoscopic, ana ɗauka cewa fipronil, desulfinyl, sulfide da sulfone (ba a gwada amide) a cikin ruwa don rage ƙwayar ƙwayar cuta ba, a kaikaice yana haifar da karuwa a cikin kwayoyin chlorophyll a (47).Matsakaicin fili shine madaidaicin tsinkaya, kuma scraper da chlorophyll a biomass sune masu canjin amsa.Ana amfani da kididdigar Fisher's C don kimanta dacewa da ƙima, ta yadda ƙimar P <0.05 ta nuna ingantaccen ƙirar ƙira (46).
Don haɓaka wakili na kariya na tushen muhalli na al'umma mai haɗari, kowane fili ya sami kashi 95% na nau'in da abin ya shafa (HC5) rarraba jiyya na nau'in na yau da kullun (SSD) da kariyar tattara hankali.An samar da saitin bayanan SSD guda uku: (i) saitin bayanan meso kawai, (ii) saitin bayanan da ke dauke da duk bayanan meso da bayanan da aka tattara daga tambayar bayanan EPA ECOTOX (https://cfpub.epa.gov/ecotox) /, shiga kan Maris 14, 2019), tsawon lokacin binciken shine kwanaki 4 ko ya fi tsayi, kuma (iii) saitin bayanan da ke dauke da duk bayanan mesoscopic da bayanan ECOTOX, wanda bayanan ECOTOX (m fallasa) ya kasu kashi mai tsanani zuwa Rawanin D. magna na yau da kullun ( 19.39) don bayyana bambance-bambance a cikin tsawon lokacin bayyanarwa kuma kusan ƙimar EC50 na yau da kullun (12).Manufar mu na samar da nau'ikan SSD da yawa shine (i) haɓaka ƙimar HC5 don kwatantawa da bayanan filin (kawai don SSDs don kafofin watsa labarai), da (ii) tantance cewa bayanan kafofin watsa labarai sun fi karɓuwa fiye da hukumomin gudanarwa don haɗawa a cikin kiwo. Ƙarfin ma'auni na rayuwa da daidaitattun saitunan albarkatun bayanai, sabili da haka yiwuwar yin amfani da nazarin mesoscopic don tsarin daidaitawa.
An haɓaka SSD don kowane saitin bayanai ta amfani da fakitin R “ssdtools” (48).Yi amfani da bootstrap (n = 10,000) don kimanta matsakaicin HC5 da tazarar amincewa (CI) daga SSD.Amsoshin haraji arba'in da tara (duk harajin da aka gano a matsayin jinsi ko nau'in) waɗanda aka haɓaka ta wannan binciken an haɗa su tare da martanin haraji 32 da aka haɗa daga binciken shida da aka buga a cikin bayanan ECOTOX, don jimlar 81 Taxon amsa za a iya amfani da su don haɓaka SSD. .Tun da ba a sami bayanai a cikin bayanan ECOTOX na amides ba, babu SSD da aka haɓaka don amides kuma an sami amsa EC50 ɗaya kawai daga binciken na yanzu.Kodayake ƙimar EC50 na rukunin sulfide ɗaya kawai aka samo a cikin bayanan ECOTOX, ɗalibin da ya kammala karatun digiri na yanzu yana da ƙimar 12 EC50.Don haka, an haɓaka SSDs don ƙungiyoyin sulfinyl.
Musamman ma'auni na HC5 na mahaɗan fipronil da aka samu daga saitin bayanan SSD na Mesocosmos kawai an haɗa su tare da bayanan filin don tantance fallasa da yuwuwar guba na mahaɗan fipronil a cikin rafukan 444 daga yankuna biyar a Amurka.A cikin taga samfurin sati 4 na ƙarshe, kowane maida hankali na mahaɗan fipronil da aka gano (ƙididdigar da ba a gano ba ba su da sifili) an raba su ta HC5, kuma ana tattara mahaɗin mahaɗin kowane samfurin don samun jimlar yawan guba na fipronil (ΣTUFipronils), inda ΣTUFipronils> 1 yana nufin guba.
Ta hanyar kwatanta haɗarin haɗari na 50% na nau'in da abin ya shafa (HC50) tare da ƙimar EC50 na wadatar taxa da aka samu daga gwajin matsakaicin membrane, an kimanta SSD da aka samu daga matsakaiciyar bayanan membrane don nuna hankalin faɗuwar al'ummomin muhalli zuwa fipronil. digiri..Ta hanyar wannan kwatancen, daidaito tsakanin hanyar SSD (ciki har da waɗancan harajin da ke da alaƙar amsa kashi) da hanyar EC50 (ciki har da duk haraji na musamman da aka lura a tsakiyar sarari) ta amfani da hanyar EC50 na auna wadatar haraji za a iya kimanta Jima'i.Alakar amsa kashi.
An ƙididdige nau'in haɗari na magungunan kashe qwari (SPEARpesticides) don bincika alaƙar da ke tsakanin yanayin kiwon lafiya na al'ummomin invertebrate da ΣTUFipronil a cikin 437 rafukan tattara invertebrate.Ma'auni na SPEARpesticides yana juyar da abun da ke ciki na invertebrates zuwa ma'auni mai yawa don ilimin lissafin halitta tare da halayen ilimin lissafi da muhalli, ta haka yana ba da hankali ga magungunan kashe qwari.Ma'anar SPEARpesticides ba ta kula da covariates na halitta (49, 50), ko da yake aikin sa zai shafi mummunan lalacewar muhalli (51).Yawancin bayanan da aka tattara akan rukunin yanar gizon don kowane haraji an haɗa su tare da mahimman ƙimar harajin da ke da alaƙa da software na ASTERICS don tantance ingancin muhallin kogin (https://gewaesser-bewertung-berechnung.de/index.php/home) html).Sannan shigo da bayanan cikin Indicate (http://systemecology.eu/indicate/) software (version 18.05).A cikin wannan software, ana amfani da bayanan halayen Turai da ma'ajin bayanai tare da sanin ilimin lissafi ga magungunan kashe qwari don canza bayanan kowane rukunin yanar gizon zuwa alamar SPEARpesticides.Kowanne daga cikin binciken yanki guda biyar yayi amfani da Janar Additive Model (GAM) [kunshin "mgcv" a cikin R(52)) don bincika alakar da ke tsakanin ma'auni na SPEARpesticides da ΣTUFipronils [log10 (X + 1) jujjuya] Associated.Don ƙarin cikakkun bayanai kan ma'aunin magungunan kashe qwari na SPEAR da kuma nazarin bayanai, da fatan za a duba Ƙarin Kayayyakin.
Ma'anar ingancin ruwa yana daidaitawa a cikin kowane mesoscopic mai gudana da duk lokacin gwaji na mesoscopic.Matsakaicin zafin jiki, pH da haɓakawa sune 13.1 ° C (± 0.27 ° C), 7.8 (± 0.12) da 54.1 (± 2.1) μS / cm (35), bi da bi.Ma'aunin carbon ɗin da aka auna a cikin ruwan kogi mai tsabta shine 3.1 mg/L.A cikin meso-view na kogin inda aka tura mai rikodin MiniDOT, narkar da iskar oxygen yana kusa da jikewa (matsakaicin> 8.0 mg/L), yana nuna cewa rafin yana yaduwa sosai.
Ana ba da kulawar inganci da bayanan tabbacin inganci akan fipronil a cikin sakin bayanan da ke rakiyar (35).A takaice dai, adadin dawo da spikes na matrix na dakin gwaje-gwaje da samfuran mesoscopic yawanci suna tsakanin jeri masu karɓa (farfadowa daga 70% zuwa 130%), ƙa'idodin IDL sun tabbatar da hanyar ƙididdigewa, kuma ɗakunan dakin gwaje-gwaje da guraben kayan aiki galibi suna tsabta Akwai kaɗan kaɗan banda waɗannan jimlolin da aka tattauna a cikin ƙarin kayan..
Saboda ƙirar tsarin, ƙaddamar da ƙaddamarwar fipronil yawanci yana ƙasa da ƙimar manufa (Figure S2) (saboda yana ɗaukar kwanaki 4 zuwa 10 don isa daidaitaccen yanayi a ƙarƙashin kyakkyawan yanayi) (30).Idan aka kwatanta da sauran mahadi na fipronil, ƙaddamar da desulfinyl da amide sun canza kadan a kan lokaci, kuma bambancin maida hankali a cikin jiyya ya fi ƙanƙanta fiye da bambanci tsakanin jiyya sai dai ƙananan maganin maganin sulfone da sulfide.Matsakaicin ma'auni na ma'auni na lokaci don kowane rukunin jiyya shine kamar haka: Fipronil, IDL zuwa 9.07μg/L;Desulfinyl, IDL zuwa 2.15μg/L;Amide, IDL zuwa 4.17μg/L;Sulfide, IDL Zuwa 0.57μg / lita;da sulfone, IDL shine 1.13μg/lita (35).A wasu rafukan, an gano mahaɗan fipronil waɗanda ba manufa ba, wato, mahadi waɗanda ba a zuga su cikin wani takamaiman magani ba, amma an san su samfuran ɓarna na fili na jiyya.Mesoscopic membranes da aka bi da su tare da fipronil na mahaifa suna da mafi yawan adadin abubuwan da ba su da niyya da aka gano (lokacin da ba a yi amfani da su azaman kayan aiki ba, su ne sulfinyl, amide, sulfide da sulfone);waɗannan na iya zama saboda tsarin samar da ƙazantattun ƙazantattun abubuwa da / ko matakai na lalata da ke faruwa a lokacin ajiyar kayan aiki da kuma (ko) a cikin gwajin mesoscopic maimakon sakamakon ƙetare.Ba a lura da yanayin raguwar raguwa a cikin jiyya na fipronil ba.Abubuwan da ba a yi niyya ba an fi gano su a cikin jiki tare da mafi girman maganin magani, amma ƙaddamarwa ya fi ƙasa da ƙaddamar da waɗannan abubuwan da ba su da manufa (duba sashe na gaba don ƙaddamarwa).Sabili da haka, tun da ba a gano abubuwan da ba su da niyya ba a cikin mafi ƙasƙanci magani na fipronil, kuma saboda ƙaddamarwar da aka gano ya fi ƙasa da tasirin sakamako a cikin mafi girman jiyya, an kammala cewa waɗannan abubuwan da ba su da manufa suna da tasiri kadan akan bincike.
A cikin gwaje-gwajen kafofin watsa labaru, benthic macroinvertebrates sun kasance masu kula da fipronil, desulfinyl, sulfone, da sulfide [Table S1;Ana ba da bayanan wadatar asali na asali a cikin nau'in bayanai masu rakiyar (35)].Fipronil amide shine kawai don tashi Rhithrogena sp.Mai guba (mai mutuwa), EC50 shine 2.05μg/L [± 10.8 (SE)].An ƙirƙiri layukan amsa kashi na nau'ikan haraji 15 na musamman.Waɗannan harajin sun nuna mace-mace a cikin kewayon tattarawar da aka gwada (Table S1), da harajin da aka yi niyya (kamar kwari) (Hoto S3) da haraji mai wadatarwa (Hoto 1) An samar da yanayin amsa kashi.Matsakaicin (EC50) na fipronil, desulfinyl, sulfone da sulfide akan kewayon haraji na musamman na kewayon haraji mai mahimmanci daga 0.005-0.364, 0.002-0.252, 0.002-0.061 da 0.005-0.043μg/L, bi da bi.Rhithrogena sp.Da Sweltsa sp.;Hoto S4) sun yi ƙasa da harajin da aka fi jurewa (kamar Micropsectra / Tanytarsus da Lepidostoma sp.) (Table S1).Dangane da matsakaicin EC50 na kowane fili a cikin Tebura S1, sulfones da sulfides sune mahadi mafi inganci, yayin da invertebrates galibi suna da ƙarancin kulawa ga desulfinyl (ban da amides).Ma'auni na yanayin yanayin yanayin gabaɗaya, kamar wadatar taxa, jimlar yawan, jimlar pentaploid da jimlar gardamar dutse, gami da taxa da wadatar wasu taxa, waɗannan ba su da yawa a cikin meso kuma ba za a iya ƙididdige su baDon haka, waɗannan alamomin muhalli sun haɗa da martanin harajin da ba a haɗa su cikin SSD ba.
Wadatar Taxa (tsutsa) tare da aikin dabaru na matakai uku na (A) fipronil, (B) desulfinyl, (C) sulfone, da (D) maida hankali na sulfide.Kowane wurin bayanai yana wakiltar tsutsa daga rafi guda a ƙarshen gwajin meso na kwanaki 30.Wadatar taxon ita ce ƙidayar haraji ta musamman a kowane rafi.Ƙimar ƙaddamarwa ita ce matsakaicin nauyin nauyi na lokaci na ƙaddamarwar da aka lura na kowane rafi da aka auna a ƙarshen gwajin kwanaki 30.Fipronil amide (ba a nuna) ba shi da dangantaka da haraji mai arziki.Lura cewa x-axis yana kan sikelin logarithmic.EC20 da EC50 tare da SE an ruwaito su a cikin Tebura S1.
A mafi girman maida hankali na dukkanin mahadi na fipronil guda biyar, ƙimar fitowar Uetridae ta ƙi.An lura da yawan ƙwayar germination (EC50) na sulfide, sulfone, fipronil, amide da desulfinyl don ragewa da 50% a yawan adadin 0.03, 0.06, 0.11, 0.78 da 0.97μg / L bi da bi (Figure 2 da Figure S5).A yawancin gwaje-gwaje na kwanaki 30, duk jiyya na fipronil, desulfinyl, sulfone da sulfide sun jinkirta, sai dai wasu ƙananan jiyya (Hoto 2), kuma an hana bayyanar su.A cikin maganin amide, abubuwan da aka tara a lokacin duk gwajin ya fi girma fiye da na sarrafawa, tare da ƙaddamar da 0.286μg / lita.Matsakaicin mafi girma (4.164μg / lita) a lokacin duk gwaje-gwajen ya hana zubar da ruwa, kuma yawan ƙwayar cuta na tsaka-tsakin magani ya kasance daidai da na ƙungiyar kulawa.(Hoto na 2).
Fitowar tarawa shine matsakaicin matsakaicin fitowar yau da kullun na kowane jiyya rage (A) fipronil, (B) desulfinyl, (C) sulfone, (D) sulfide da (E) amide a cikin rafi mai sarrafawa Matsakaicin matsakaicin fitowar yau da kullun na membrane.Sai dai don sarrafawa (n = 6), n = 1. Ƙimar ƙaddamarwa ita ce ma'auni mai nauyin lokaci na ƙaddarar da aka lura a cikin kowane kwarara.
Tsarin amsa kashi yana nuna cewa, ban da asarar haraji, canje-canjen tsari a matakin al'umma.Musamman, a cikin kewayon ƙaddamarwar gwaji, yawan may (Hoto S3) da yawan haraji (Hoto 1) sun nuna alaƙar amsa kashi-kashi tare da fipronil, desulfinyl, sulfone, da sulfide.Saboda haka, mun bincika yadda waɗannan canje-canjen tsarin ke haifar da canje-canje a cikin ayyukan al'umma ta hanyar gwada kasidar abinci mai gina jiki.Bayyanar invertebrates na ruwa zuwa fipronil, desulfinyl, sulfide da sulfone yana da mummunar tasiri kai tsaye a kan biomass na scraper (Hoto 3).Domin sarrafa mummunan tasirin fipronil akan biomass na scraper, scraper shima ya yi mummunan tasiri ga chlorophyll a biomass (Hoto na 3).Sakamakon waɗannan ƙididdiga mara kyau na hanya shine haɓakar haɓakawa a cikin chlorophyll a yayin da haɓakar fipronil da masu lalata suna ƙaruwa.Waɗannan samfuran hanyoyin shiga tsakani cikakke suna nuna cewa ƙara lalacewa na fipronil ko fipronil yana haifar da haɓakar adadin chlorophyll a (Hoto na 3).An ɗauka a gaba cewa tasirin kai tsaye tsakanin fipronil ko raguwar ƙwayar cuta da chlorophyll biomass ba komai bane, saboda mahaɗan fipronil sune magungunan kashe qwari kuma suna da ƙarancin guba kai tsaye ga algae (alal misali, EPA m ƙarancin ƙwayar shuka ba na jijiyoyin jini ba shine 100μg / L. fipronil, ƙungiyar disulfoxide, sulfone da sulfide; https://epa.gov/pesticide-science-and-assessing-pesticide-risks/aquatic-life-benchmarks-and-ecological-risk), Duk sakamakon (samfurori masu inganci) sun goyi bayan wannan. hasashe.
Fipronil na iya rage haɓakar halittu (tasirin kai tsaye) na kiwo (kungiyar scraper tsutsa ce), amma ba shi da wani tasiri kai tsaye akan biomass na chlorophyll a.Koyaya, tasirin fipronil kaikaice mai ƙarfi shine ƙara haɓakar chlorophyll a sakamakon ƙarancin kiwo.Kibiya tana nuna daidaitacciyar hanyar haɗin kai, kuma alamar ragi (-) tana nuna alkiblar ƙungiya.* Yana nuna darajar mahimmancin.
SSD guda uku (tsakiyar Layer kawai, tsakiyar Layer da bayanan ECOTOX, da tsakiyar Layer da bayanan ECOTOX da aka gyara don bambance-bambance a cikin tsawon lokacin bayyanar) sun haifar da ƙima daban-daban na HC5 (Table S3), amma sakamakon yana cikin kewayon SE.A cikin sauran wannan binciken, za mu mai da hankali kan bayanan SSD tare da duniyar meso kawai da ƙimar HC5 mai alaƙa.Don ƙarin cikakken bayanin waɗannan kimantawa na SSD guda uku, da fatan za a koma zuwa ƙarin kayan (Tables S2 zuwa S5 da Figures S6 da S7).Mafi dacewa da rarraba bayanai (mafi ƙasƙanci daidaitaccen ma'aunin bayanin Akaike) na mahaɗan fipronil huɗu (Hoto 4) waɗanda aka yi amfani da su kawai a cikin taswirar SSD mai ƙarfi shine log-gumbel na fipronil da sulfone, da weibull na sulfide And desulfurized γ ( Table S3).Ana ba da rahoton ƙimar HC5 da aka samu don kowane fili a cikin Hoto 4 don duniyar meso kawai, kuma a cikin Tebura S3 an ba da rahoton ƙimar HC5 daga duk bayanan bayanan SSD guda uku.Ma'aunin HC50 na fipronil, sulfide, sulfone da desulfinyl kungiyoyin [22.1 ± 8.78 ng/L (95% CI, 11.4 zuwa 46.2), 16.9 ± 3.38 ng/L (95% CI, 11.2 zuwa 24.0), 8 8 8 2.66 ng/L (95% CI, 5.44 zuwa 15.8) da 83.4 ± 32.9 ng/L (95% CI, 36.4 zuwa 163)] Waɗannan mahadi sun fi ƙasa da wadatar taxa EC50 ( jimlar adadin haraji na musamman) (Table S1) ; bayanin kula a cikin ƙarin kayan aikin shine micrograms kowace lita).
A cikin gwajin meso-sikelin, lokacin da aka fallasa (A) fipronil, (B) dessulfinyl fipronil, (C) fipronil sulfone, (D) fipronil sulfide na kwanaki 30, an kwatanta jin daɗin jinsunan shine darajar EC50 na taxon.Layin shuɗi mai shuɗi yana wakiltar 95% CI.Layin kwance a kwance yana wakiltar HC5.Ƙimar HC5 (ng / L) na kowane fili shine kamar haka: Fipronil, 4.56 ng / L (95% CI, 2.59 zuwa 10.2);Sulfide, 3.52 ng/L (1.36 zuwa 9.20);Sulfone, 2.86 ng / Lita (1.93 zuwa 5.29);da sulfinyl, 3.55 ng/lita (0.35 zuwa 28.4).Lura cewa x-axis yana kan sikelin logarithmic.
A cikin binciken yanki guda biyar, Fipronil (iyaye) an gano su a cikin 22% na maki 444 na samfurin (Table 1).Gano mita na florfenib, sulfone da amide yana kama da (18% zuwa 22% na samfurin), yawan gano sulfide da desulfinyl ya ragu (11% zuwa 13%), yayin da sauran samfurori na lalata suna da yawa.Kadan (1% ko ƙasa da haka) ko ba a taɓa ganowa ba (Table 1)..Ana gano Fipronil akai-akai a kudu maso gabas (52% na shafuka) kuma aƙalla akai-akai a arewa maso yamma (9% na shafukan), wanda ke nuna bambancin amfani da benzopyrazole da yuwuwar raunin rafi a duk faɗin ƙasar.Masu lalata yawanci suna nuna irin wannan tsarin yanki, tare da mafi girman saurin ganowa a kudu maso gabas da mafi ƙanƙanta a arewa maso yamma ko gabar tekun California.Ƙididdigar ƙididdiga na fipronil shine mafi girma, biye da mahaifa fipronil (kashi 90% na 10.8 da 6.3 ng / L, bi da bi) (Table 1) (35).An ƙaddara mafi girma na fipronil (61.4 ng / L), disulfinyl (10.6 ng / L) da sulfide (8.0 ng / L) a kudu maso gabas (a cikin makonni hudu na ƙarshe na samfurin).An ƙaddara mafi girman taro na sulfone a yamma.(15.7 ng / L), amide (42.7 ng / L), dessulfinyl flupirnamide (14 ng / L) da fipronil sulfonate (8.1 ng / L) (35).Florfenide sulfone shine kawai fili wanda aka lura ya wuce HC5 (Table 1).Matsakaicin ΣTUFipronils tsakanin yankuna daban-daban sun bambanta sosai (Table 1).Matsakaicin ΣTUFipronils na ƙasa shine 0.62 (duk wurare, duk yankuna), kuma rukunin 71 (16%) suna da ΣTUFipronils> 1, yana nuna cewa yana iya zama mai guba ga macroinvertebrates benthic.A cikin hudu daga cikin yankuna biyar da aka yi nazari (sai dai Midwest), akwai dangantaka mai mahimmanci tsakanin SPEARpesticides da ΣTUFipronil, tare da daidaitawa R2 daga 0.07 tare da bakin tekun California zuwa 0.34 a kudu maso gabas (Figure 5).
* Abubuwan da aka yi amfani da su a cikin gwaje-gwajen mesoscopic.†ΣTUFipronils, tsaka-tsakin jimlar raka'a mai guba [wanda aka lura da yanayin filin na mahaɗan fipronil huɗu / haɗarin haɗarin kowane fili daga kashi na biyar na nau'in cutar SSD (Hoto 4)] Don samfuran mako-mako na fipronil, 4 na ƙarshe An ƙididdige makonni na samfuran magungunan kashe qwari da aka tattara a kowane rukunin yanar gizon.‡Yawan wuraren da ake auna magungunan kashe qwari.§Kashi 90th na kashi ya dogara ne akan matsakaicin maida hankali da aka gani akan wurin a cikin makonni 4 na ƙarshe na samfurin maganin kwari.tare da adadin samfuran da aka gwada.Yi amfani da 95% CI na ƙimar HC5 (Hoto 4 da Tebura S3, kawai meso) don ƙididdige CI.An bincika Dechloroflupinib a duk yankuna kuma ba a taɓa samun su ba.ND, ba a gano shi ba.
Ƙungiyar mai guba ta Fipronil ita ce ma'auni na fipronil wanda aka auna ta hanyar ƙimar HC5 na musamman, wanda SSD ya samo daga gwajin watsa labaru (duba Hoto 4).Layin Baƙar fata, ƙirar ƙari gama gari (GAM).Layin jajayen ja yana da CI na 95% don GAM.An canza ΣTUFipronils zuwa log10 (ΣTUFipronils+1).
Abubuwan da ke haifar da fipronil a kan nau'in ruwa marasa manufa an rubuta su da kyau (15, 21, 24, 25, 32, 33), amma wannan shine binciken farko wanda yake da hankali a cikin yanayin dakin gwaje-gwaje.An fallasa al'ummomin harajin zuwa mahaɗan fipronil, kuma an fitar da sakamakon a kan sikelin nahiyoyi.Sakamakon gwajin mesocosmic na kwanaki 30 na iya haifar da ƙungiyoyin kwari na ruwa na 15 masu hankali (Table S1) tare da maida hankali da ba a ba da rahoto ba a cikin wallafe-wallafen, daga cikinsu akwai ƙananan ƙwayoyin ruwa a cikin bayanan mai guba (53, 54).Takamaiman matakan amsa haraji (irin su EC50) suna nunawa a cikin sauye-sauyen matakin al'umma (kamar wadatar haraji kuma yana iya tashi asara mai yawa) da canje-canjen aiki (kamar ɓangarorin abinci mai gina jiki da canje-canjen bayyanar).An fitar da tasirin duniyar mesoscopic zuwa filin.A cikin hudu daga cikin wuraren bincike guda biyar a Amurka, an daidaita ma'aunin fipronil da aka auna a filin tare da raguwar yanayin yanayin ruwa a cikin ruwa mai gudana.
Ƙimar HC5 na 95% na nau'in nau'in a cikin gwajin matsakaici na membrane yana da tasirin kariya, yana nuna cewa gaba ɗaya al'ummomin invertebrate na ruwa sun fi kula da mahadi na fipronil fiye da yadda aka fahimta a baya.Ƙimar HC5 da aka samu (florfenib, 4.56 ng / lita; desulfoxirane, 3.55 ng / lita; sulfone, 2.86 ng / lita; sulfide, 3.52 ng / lita) sau da yawa (florfenib) zuwa sau uku fiye da tsari na girma (desulfinyl). ) a ƙasa na EPA na yau da kullum invertebrate benchmark [fipronil, 11 ng / lita;desulfinyl, 10,310 ng / lita;sulfone, 37 ng / lita;da sulfide, don 110 ng/lita (8)].Gwaje-gwaje na Mesoscopic sun gano ƙungiyoyi da yawa waɗanda ke da mahimmanci ga fipronil maimakon waɗanda EPA na yau da kullun invertebrate benchmark (kungiyoyin 4 da suka fi dacewa da fipronil, nau'i-nau'i na 13 na desulfinyl, 11 nau'i na sulfone da 13 nau'i-nau'i) Sulfide sensitivity) (Hoto 4 da). tebur) S1).Wannan ya nuna cewa alamomi ba zai iya kare nau'ikan da yawa waɗanda suma sun lura a cikin tsakiyar duniya, waɗanda kuma sun yadu a cikin yanayin halittu masu ruwa.Bambanci tsakanin sakamakon mu da ma'auni na yanzu shine yawanci saboda rashin bayanan gwajin cutar fipronil wanda ya dace da nau'ikan harajin kwari na ruwa, musamman lokacin da lokacin fallasa ya wuce kwanaki 4 kuma fipronil ya ragu.A lokacin gwajin mesocosmic na kwanaki 30, yawancin kwari a cikin al'ummar invertebrate sun fi kulawa da fipronil fiye da kwayoyin gwaji na yau da kullum Aztec (crustacean), ko da bayan gyara Aztec EC50 na Teike ya sa ya zama iri ɗaya bayan babban canji.(Yawanci awanni 96) zuwa lokacin fallasa na yau da kullun (Hoto S7).An cimma ingantacciyar yarjejeniya tsakanin matsakaicin gwajin membrane da binciken da aka ruwaito a cikin ECOTOX ta amfani da daidaitaccen kwayar cutar Chironomus dilutus (kwari).Ba abin mamaki ba ne cewa kwari na ruwa suna da damuwa musamman ga magungunan kashe qwari.Ba tare da daidaita lokacin bayyanarwa ba, gwajin meso-sikelin da cikakkun bayanai na bayanan ECOTOX sun nuna cewa yawancin haraji da aka lura sun fi dacewa da mahadi na fipronil fiye da Clostridium diluted (Figure S6).Duk da haka, ta hanyar daidaita lokacin bayyanar, Dilution Clostridium shine mafi mahimmancin kwayoyin halitta ga fipronil (iyaye) da sulfide, kodayake ba shi da hankali ga sulfone (Figure S7).Waɗannan sakamakon suna kwatanta mahimmancin haɗa nau'ikan halittu masu ruwa da yawa (ciki har da ƙwari da yawa) don samar da ainihin adadin magungunan kashe qwari wanda zai iya kare halittun ruwa.
Hanyar SSD na iya kare harajin da ba kasafai ba ko rashin hankali wanda EC50 ba za a iya tantance shi ba, kamar Cinygmula sp., Isoperla fulva da Brachycentrus americanus.Ma'aunin EC50 na yawan haraji kuma yana iya tashi da yawa yana nuna canje-canje a cikin abubuwan al'umma sun yi daidai da ƙimar HC50 na SSD na fipronil, sulfone da sulfide.Yarjejeniyar tana goyan bayan ra'ayi mai zuwa: Hanyar SSD da ake amfani da ita don samun ƙofa na iya kare al'umma gaba ɗaya, gami da harajin da ba kasafai ba ko rashin fahimta a cikin al'umma.Ƙofar kwayoyin halittun ruwa da aka ƙayyade daga SSDs dangane da ƴan haraji kawai ko harajin da ba su da hankali na iya zama rashin isa sosai wajen kare muhallin ruwa.Wannan shine yanayin desulfinyl (Hoto S6B).Saboda rashin bayanai a cikin bayanan ECOTOX, EPA na yau da kullun invertebrate tushe na asali shine 10,310 ng/L, wanda shine umarni huɗu na girma sama da 3.55 ng/L na HC5.Sakamakon saitin amsa taxo daban-daban da aka samar a cikin gwaje-gwajen mesoscopic.Rashin bayanan mai guba yana da matsala musamman ga mahadi masu lalacewa (Hoto S6), wanda zai iya yin bayanin dalilin da yasa ma'auni na nazarin halittu na ruwa don sulfide da sulfide kusan sau 15 zuwa 30 ba su da hankali fiye da ƙimar SSD HC5 dangane da sararin samaniyar China.Amfanin hanyar membrane na matsakaici shine cewa ana iya ƙayyade ƙimar EC50 da yawa a cikin gwaji guda ɗaya, wanda ya isa ya samar da cikakkiyar SSD (misali, desulfinyl; Hoto 4B da Figures S6B da S7B), kuma suna da tasiri mai mahimmanci. a kan haraji na dabi'a na kariyar muhalli Amsoshi da yawa.
Gwaje-gwajen Mesoscopic sun nuna cewa fipronil da samfuran lalatawar sa na iya samun sakamako mai lahani na zahiri da na kai tsaye akan ayyukan al'umma.A cikin gwajin mesoscopic, dukkanin mahadi na fipronil guda biyar sun bayyana sun shafi bayyanar kwari.Sakamakon kwatancen tsakanin mafi girma da mafi ƙasƙanci (hanawa da haɓaka fitowar mutum ko canje-canje a lokacin fitowar) sun dace da sakamakon da aka ruwaito a baya na gwajin meso ta amfani da bifenthrin na kwari (29).Bayyanar manya yana ba da mahimman ayyuka na muhalli kuma ana iya canza su ta hanyar gurɓatawa kamar fipronil (55, 56).Fitowar lokaci guda ba wai kawai tana da mahimmanci ga haifuwar kwari da dagewar jama'a ba, har ma da samar da manyan kwari, waɗanda za a iya amfani da su azaman abinci ga dabbobin ruwa da na ƙasa (56).Hana bullowar tsiro na iya yin illa ga mu’amalar abinci tsakanin halittun ruwa da magudanan ruwa, da kuma yada tasirin gurbacewar ruwa zuwa yanayin halittun kasa (55, 56).Rage yawan abubuwan scrapers (kwari masu cin algae) da aka lura a cikin gwajin meso-sikelin ya haifar da raguwar amfani da algae, wanda ya haifar da karuwa a cikin chlorophyll a (Figure 3).Wannan trophic cascade yana canza canjin carbon da nitrogen a cikin gidan yanar gizon abinci na ruwa, kama da binciken da ya kimanta tasirin pyrethroid bifenthrin akan al'ummomin benthic (29).Sabili da haka, phenylpyrazoles, irin su fipronil da samfuran lalacewa, pyrethroids, da kuma watakila wasu nau'in maganin kwari, na iya haɓaka haɓakar ƙwayoyin algal biomass a kaikaice da kuma lalata carbon da nitrogen a cikin ƙananan koguna.Sauran tasirin na iya ƙarawa zuwa lalata hawan carbon da nitrogen tsakanin halittun ruwa da na ƙasa.
Bayanan da aka samu daga gwajin matsakaicin membrane ya ba mu damar kimanta mahimmancin yanayin muhalli na fipronil mahadi da aka auna a cikin manyan nazarin filin da aka gudanar a yankuna biyar na Amurka.A cikin ƙananan rafukan 444, 17% na matsakaicin matsakaici na ɗaya ko fiye na fipronil mahadi (matsakaicin sama da makonni 4) ya wuce ƙimar HC5 da aka samu daga gwajin watsa labarai.Yi amfani da SSD daga gwajin meso-sikelin don canza ma'aunin fipronil fili maida hankali zuwa ma'auni mai alaƙa da guba, wato, jimlar raka'a masu guba (ΣTUFipronils).Ƙimar 1 tana nuna guba ko tarin bayyanar fipronil fili ya zarce sanannen kariyar nau'ikan da ya kai 95%.Muhimman dangantakar dake tsakanin ΣTUFipronil a cikin hudu daga cikin yankuna biyar da kuma SPEARpesticides nuna alama na invertebrate al'umma kiwon lafiya ya nuna cewa fipronil iya adversely rinjayar benthic invertebrate al'ummomi a cikin koguna a mahara yankuna na Amurka.Waɗannan sakamakon suna goyan bayan hasashen Wolfram et al.(3) Haɗarin maganin kwari na phenpyrazole zuwa saman ruwa a cikin Amurka ba a fahimta sosai ba saboda tasirin kwari a cikin ruwa yana faruwa a ƙasa da ƙa'idar ƙa'ida ta yanzu.
Yawancin rafukan da ke da abun ciki na fipronil sama da matakin mai guba suna cikin yankin kudu maso gabas (https://webapps.usgs.gov/rsqa/#!/region/SESQA).Ƙimar da ta gabata na yankin ba wai kawai ta tabbatar da cewa fipronil shine babban damuwa da ke shafar tsarin al'umma na invertebrate a cikin raƙuman ruwa ba, amma har ma da ƙananan iskar oxygen, ƙara yawan abubuwan gina jiki, canje-canje masu gudana, lalata mazaunin gida, da sauran magungunan kashe qwari da kuma nau'in gurɓataccen abu yana da mahimmanci. tushen damuwa (57).Wannan cakudewar damuwa ya yi daidai da “ciwon kogin birni”, wanda shine lalacewar yanayin kogin da aka saba gani dangane da amfani da filaye na birane (58, 59).Alamomin amfani da filaye na birane a yankin Kudu maso Gabas na karuwa kuma ana sa ran za su karu yayin da yawan al'ummar yankin ke karuwa.Ana sa ran tasirin ci gaban birane da magungunan kashe qwari a nan gaba zai karu (4).Idan birane da kuma amfani da fipronil ya ci gaba da girma, amfani da wannan maganin kashe qwari a birane na iya ƙara rinjayar al'ummomin rafi.Ko da yake ƙididdiga ta ƙarshe ta ƙare da cewa amfani da magungunan kashe qwari na noma yana barazana ga yanayin rafi na duniya (2, 60), muna ɗauka cewa waɗannan ƙididdiga sun raina tasirin magungunan kashe qwari gaba ɗaya ta hanyar ban da amfani da birane.
Matsaloli daban-daban, gami da magungunan kashe qwari, na iya shafar al'ummomin macroinvertebrate a cikin magudanan ruwa masu tasowa (birane, amfanin gona da gauraye ƙasa) kuma suna iya alaƙa da amfani da ƙasa (58, 59, 61).Ko da yake wannan binciken yayi amfani da SPEARpesticides nuna alama da ruwa-kwayoyin-takamaiman fipronil toxicity halaye don rage girman tasiri na rikice-rikice dalilai, aikin na SPEARpesticides nuna alama na iya zama da lalacewa ta hanyar lalata muhalli, da kuma fipronil za a iya kwatanta da sauran Pesticide alaka (4, 17, 51, 57).Duk da haka, wani nau'i mai yawa na damuwa da aka haɓaka ta amfani da ma'auni na filin daga binciken yanki biyu na farko (Midwestern da Kudu maso Gabas) ya nuna cewa magungunan kashe qwari wani muhimmin damuwa ne ga yanayin al'umma na macroinvertebrate a cikin koguna.A cikin waɗannan samfuran, mahimman bayanai masu mahimmanci sun haɗa da magungunan kashe qwari (musamman bifenthrin), abubuwan gina jiki da halayen muhalli a mafi yawan rafukan noma a cikin Midwest, da magungunan kashe qwari (musamman fipronil) a yawancin biranen kudu maso gabas.Canje-canje a cikin iskar oxygen, abubuwan gina jiki da kwarara (61, 62).Sabili da haka, ko da yake nazarin yanki yana ƙoƙari ya magance tasirin abubuwan da ba su da magungunan kashe qwari a kan alamun amsawa da kuma daidaita alamun tsinkaya don kwatanta tasirin fipronil, sakamakon filin wannan binciken yana goyan bayan ra'ayin fipronil.) Ya kamata a yi la'akari da daya daga cikin mafi tasiri tushen matsi a cikin kogin Amurka, musamman a kudu maso gabashin Amurka.
Ba kasafai ake yin rubuce-rubucen faruwar lalata magungunan kashe qwari a cikin muhalli ba, amma barazanar ga halittun ruwa na iya zama mafi illa fiye da na iyaye.A cikin yanayin fipronil, nazarin filin da gwaje-gwaje na meso-sikelin sun nuna cewa samfurori na lalata suna da yawa kamar yadda iyaye suke a cikin rafukan da aka samo kuma suna da irin wannan ko mafi girma (Table 1).A cikin gwajin matsakaicin membrane, fluorobenzonitrile sulfone shine mafi guba na samfuran lalata magungunan kashe qwari da aka yi nazari, kuma ya fi guba fiye da mahallin mahaifa, kuma an gano shi a mitar mai kama da na mahaifa.Idan kawai an auna magungunan kashe qwari na iyaye, ƙila ba za a iya lura da abubuwan da suka faru na guba ba, kuma ƙarancin ƙarancin bayanan guba yayin lalata ƙwayoyin cuta yana nufin cewa ana iya yin watsi da faruwar su da sakamakonsu.Alal misali, saboda rashin samun bayanai game da guba na kayayyakin lalata, an gudanar da cikakken kima na magungunan kashe qwari a cikin rafukan Swiss, ciki har da 134 kayayyakin lalata magungunan kashe qwari, kuma kawai mahaifar mahaifa an yi la'akari da shi a matsayin mahaifar mahaifa a cikin kimantawar haɗarin ecotoxicological.
Sakamakon wannan ƙididdigar haɗarin muhalli ya nuna cewa fipronil mahadi suna da mummunan tasiri akan lafiyar kogin, don haka za a iya la'akari da cewa za a iya lura da mummunar tasiri a ko'ina inda mahadi na fipronil suka wuce matakin HC5.Sakamakon gwaje-gwaje na mesoscopic masu zaman kansu ne daga wuri, yana nuna cewa ƙaddamar da fipronil da samfurori na lalacewa a yawancin harajin rafi yana da ƙasa fiye da yadda aka rubuta a baya.Mun yi imanin cewa ana iya faɗaɗa wannan binciken zuwa protobiota a cikin rafukan da ba su da kyau a ko'ina.Sakamakon gwajin meso-sikelin an yi amfani da shi a kan manyan nazarin filin (kananan rafukan 444 da suka ƙunshi birane, noma, da gaurayen amfani da ƙasa a cikin manyan yankuna biyar na Amurka), kuma an gano cewa yawan rafuka da yawa. Inda aka gano fipronil ana sa ran zama Sakamakon guba ya nuna cewa waɗannan sakamakon na iya ƙara zuwa wasu ƙasashe inda ake amfani da fipronil.A cewar rahotanni, adadin mutanen da ke amfani da Fipronil yana karuwa a Japan, Birtaniya da Amurka (7).Fipronil yana nan a kusan kowace nahiya, gami da Ostiraliya, Amurka ta Kudu da Afirka (https://coherentmarketinsights.com/market-insight/fipronil-market-2208).Sakamakon binciken meso-to-filin da aka gabatar a nan yana nuna cewa yin amfani da fipronil na iya samun mahimmancin muhalli a duniya.
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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
Nazarin ya nuna cewa magungunan kashe qwari na yau da kullun waɗanda ake yawan ganowa a cikin kogunan Amurka sun fi guba fiye da yadda ake tsammani a baya.
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
Nazarin ya nuna cewa magungunan kashe qwari na yau da kullun waɗanda ake yawan ganowa a cikin kogunan Amurka sun fi guba fiye da yadda ake tsammani a baya.
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