I-methylene blue kwindalo: isiphelo sayo, ubuthi kwizinto eziphila emanzini, namanzi amdaka ngokomxholo

Zimbini iintlobo ezahlukeneyo zoncwadi lwenzululwazi ezisebenzisa igama elithi methylene blue. Eyokuqala luncwadi lokulinganisa okwenzeka kwindalo: lunqabile, lunamanani, yaye luzele ziinkcazelo ezibeka imida kwiziphumo. Olwesibini luncwadi lonyango lwamanzi: lukhulu kakhulu, luzithembile, yaye phantse lonke lusekelwe kwizinyibiliko ezenziweyo ezixutywe elabhoratri. Ukubhidanisa olwesibini nolokuqala yeyona mpazamo iphambili kulo mba. Iphepha lophando elisusa i-95 pesenti yedayi kwiflaski eyongezwe idayi libonise uphawu lwemathiriyeli, hayi uxinaniso olukhoyo kwindalo.

Eli nqaku lizigcina zahlukene ezi ntlobo zimbini. Kuqala sijonga isiphelo semolekyuli emanzini, emva koko iziphumo zobuthi ezilinganisiweyo, size sijonge ukuba amanani amanzi amdaka achaza ntoni ngokwenene.

Isiphelo: i-cation enyibilikayo enamathela kwizinto eziqinileyo

I-methylene blue inyibilika lula yaye ihlala inentlawulo yombane ethabathayo kuluhlu oluqhelekileyo lwe-pH kwindalo. Iingqokelela zeenkcukacha zesalathiso zidwelisa ukunyibilika okukufutshane ne-43,600 mg/L kwi-25 C, yaye uphononongo olunzulu lowama-2025 lweempawu zayo eziphathelele ukukhanya luqinisekisa ukuba idayi ikakhulu ikwimo ye-cation ye-MB kuluhlu olumalunga ne-pH 3.5 ukuya kwi-11.5. Ngoko ke ukuguquka kwayo ibe ngumphunga iphuma emanzini kuncinane kangangokuba akubalulekanga. Eyona nkqubo ibalulekileyo kukubambeka kwayo kwezinye izinto.

Ngenxa yokuba iyi-cation, idayi ibophelela ngamandla kwimiphezulu enentlawulo yombane ethabathayo engaphantsi kweqanda: udongwe, intlenga, udaka lonyango lwamanzi, nezinto eziphilayo okanye ezivela kuzo. Uphando lwakudala lomhlaba olucatshulwe kwiirekhodi zesalathiso lwafumanisa ukubambeka ngamandla kwizinto eziphilayo okanye ezivela kuzo, kwi-montmorillonite nakwi-kaolinite, kusale inxalenye encinane kuphela enokukhutshwa. Izifundo zotshintshiselwano kudongwe zibonisa ngokuthe ngqo ukuba le nkqubo lutshintshiselwano lwee-cation oluxhomekeke kwi-pH, kwii-ion ezikhuphisanayo, nakuxinaniso lwedayi. Uqikelelo lwe-Koc oludla ngokucatshulwa, olusondele kwi-8,000, luqikelela isiphumo esifanayo, kodwa maluthathwe njengoqikelelo lwedayi ene-ion kunokuba lube lixabiso elisisigxina elilinganisiweyo. Ubudlelwane obuqhelekileyo be-Koc benzelwa iikhompawundi zekhabhoni ezingenantlawulo yombane yaye abuhambelani kakuhle nee-ion.

Udaka olusebenzayo lonyango lwamanzi luyayibamba idayi ngale ndlela inye, nokuba akukho kubola okubangelwa zizinto eziphilayo. Izifundo zebhetshi ezisebenzisa udaka olomisiweyo zaxela izakhono ze-Langmuir ezikufutshane ne-256 mg yedayi ngegram yodaka kwi-pH 7, yaye uphando lwamva ngezinto ze-polymer ezingaphandle kweeseli lwafikelela malunga ne-366 mg/g, ulungelelwano lufikelelwa ngemizuzu. Ezo zizakhono ezilinganiselwe elabhoratri, hayi amazinga okususa idayi kwiziko lonyango lwamanzi, kodwa zichaza ukuba kutheni umbala wedayi unokunyamalala emanzini uye kwizinto eziqinileyo ngoxa imolekyuli ngokwayo isekhona.

Ukukhanya kwelanga kukodwa akuyondlela ethembekileyo yokuyiphelisa. Uphononongo lwezifundo zonyango lwe-methylene blue luxela uvavanyo olunye olwasusa kuphela malunga ne-8 pesenti emva kweeyure ezili-10 zokwahlulwa ngokukhanya ngaphandle kwe-catalyst, kunye novavanyo oluninzi lolawulo lokukhanya okubonakalayo olwalubonise ilahleko engabalulekanga. Musa ukunika idayi ixesha elinye elisebenza kuzo zonke iimeko lokuncipha iye kwisiqingatha phantsi kokukhanya kwelanga. Amandla okukhanya okufikayo, i-pH, ioksijini, izinto eziqinileyo ezijingayo emanzini, nokuzivuselela kwayo ngokukhanya konke kuyasitshintsha isiphumo.

Iirekhodi zokubola okubangelwa zizinto eziphilayo zinomsantsa ophambili. Akukho siphumo se-OECD 301 esichazwe ngokucacileyo sokuvavanya ukubola lula kwe-methylene blue esulungekileyo esafunyanwayo xa kwakulungiselelwa eli nqaku. Amaphepha ophando lokuqala onyango lwamanzi adla ngokuyibiza idayi ngokuba ngummeli weedayi ezixhathisa ukubola okubangelwa zizinto eziphilayo, yaye amanye amaxwebhu okhuseleko ayichaza njengengaboli lula, kodwa akukho nanye kwezo enokuthatha indawo yedatha yovavanyo olusemgangathweni. Iinkcubeko zeebhaktiriya ezikhethiweyo neengqimba zeentsholongwane zinokususa umbala okanye ziguqule idayi phantsi kweemeko ezilungiselelwe kakuhle. Ngoko ke ingxelo enokuxhaswa inomda: idla ngokuchazwa njengexhathisayo, kungekho xabiso liqinisekisiweyo lokuphumelela okanye lokungaphumeleli kuvavanyo olusemgangathweni lifunyenweyo. Ikhemistri yokuguquka kwayo iqondwa ngcono. Ukususwa kwamaqela e-N-methyl nge-oxidation kuhamba malunga nokusuka kwidayi yokuqala kuye kwi-Azure B, Azure A, Azure C, nakwi-thionine, ngoxa iimeko ze-reduction ziguqula idayi ibe yi-leucomethylene blue engenambala. Ngoko ke amanzi acacileyo emva kwe-reduction abubobungqina bokutshatyalaliswa. Undoqo we-phenothiazine unokuhlala unjalo nasemva kokuba umbala unyamalele.

Ubuthi kwizinto eziphila emanzini: iziphumo ezilinganisiweyo, ezinemeko ezichaziweyo

Izifundo zobuthi be-methylene blue kwindalo ezisebenzisa imigangatho zimbalwa, yaye iziphumo zamva zahluke kwamanye amaxabiso oovimba bedatha amadala ngamaxesha amaninzi aphindwe ngeshumi. Inani ngalinye elingezantsi lifuna uhlobo lwesidalwa, ixesha, nesiphumo esilinganisiweyo, kuba ukususa ezo nkcukacha kuko okusasaza ukubhideka.

Esona siphumo samva esibonisa ubuthathaka obukhulu sesentakumba yamanzi. Uphononongo lowama-2023 lweziphumo zobuthi kwi-Daphnia magna lwaxela i-EC50 yokungakwazi ukuhamba emva kweeyure ezingama-48 eyi-61.5 micrograms ngelitha (0.062 mg/L), ne-LC50 yeeyure ezingama-24 eyi-0.149 mg/L, kunye neziphumo kwimisebenzi yomzimba nasekuzaleni xa uxinaniso lungaphezu kwe-4.7 micrograms ngelitha. Olo xinaniso lokugqibela linqanaba apho isiphumo sabonwa khona ngokobalo lwababhali, hayi uxinaniso olungenasiphumo olumiselwe yimigaqo yolawulo. Kodwa umqondiso uwonke ucacile: ii-cladoceran ziyasabela kuxinaniso olungaphantsi kakhulu kwamanqanaba aqhelekileyo ongezwa kwiimvavanyo zaselabhoratri.

Idatha yeentlanzi ixhomekeke kwiimeko. Imibungu yeentlanzi ze-fathead minnow echanabekiswe kwiimvavanyo zexesha elifutshane neliphakathi yanika amaxabiso e-LC50 eeyure ezingama-96 ayi-45 mg/L kwi-20 C nayi-15 mg/L kwi-25 C, kunye namaxabiso eempembelelo eziqhubekayo kwiintsuku ezisixhenxe asondele kwi-2.1 mg/L ngokuphila nakwi-0.6 mg/L ngokukhula phantsi kokukhanya kwaselabhoratri. Iqondo lobushushu nokukhanya zatshintsha isiphumo, nto leyo ebalulekileyo kuba umbala wedayi ngokwawo utshintsha ukungena kokukhanya emanzini.

Izinto eziphilayo ezivelisa ukutya okusisiseko zinamaxabiso akwizinga elisezantsi lamanani anedijithi enye kuthotho olunye olufana novavanyo lwe-OECD. Ukuchanabeka kweeyure ezingama-24 ukuya kwezingama-96 kwanika amaxabiso e-EC50 ancipha ukusuka malunga ne-62 ukuya kwi-5.4 mg/L kwi-Chlorella vulgaris, nokusuka malunga ne-5.8 ukuya kwi-1.1 mg/L kwi-Spirulina platensis, yona eyi-cyanobacterium kunokuba ibe lulwelwe lwe-eukaryote. Uvavanyo olufutshane lwebhaktiriya yaselwandle i-Vibrio harveyi lwalinganisa i-EC50 yokukhanya okuveliswa zizinto eziphilayo kwimizuzu eli-15, esondele kwi-18 mg/L kwidayi engahlulwanga, nto leyo echaza ukusabela kwebhaktiriya kwexesha elifutshane, hayi ukuthintelwa kokusebenza kodaka lonyango lwamanzi.

Esinye isiphumo sifanele ukuqwalaselwa ngokukhethekileyo ziinjineli zonyango lwamanzi. Iintsholongwane ezenza i-oxidation ye-ammonia zabonisa umahluko omkhulu kubuthathaka bazo: i-archaeon i-Nitrosopumilus maritimus yalahlekelwa malunga ne-65 pesenti yomsebenzi wayo we-oxidation ye-ammonia kwi-0.010 mg/L, ngoxa ibhaktiriya i-Nitrosococcus oceani yayifuna malunga ne-10 mg/L ukuze kubekho isiphumo esilinganayo kwiimvavanyo ezithelekisayo zokuthintelwa kokusebenza. Ezi ziingqwalaselo zepesenti yokuthintelwa kokusebenza kunokuba zibe ngamaxabiso e-IC50, kodwa zibonisa ukuba ukuguqulwa kwe-ammonia ibe yi-nitrite ne-nitrate yinkqubo efanele ukukhuselwa kuwo nawaphi na amanzi akhutshwayo anale dayi.

Umxholo wolawulo unomda. Akukho luhlelo lwe-EU oluhambelanisiweyo nolungqinisisiweyo lobungozi emanzini, okanye i-PNEC kawonke-wonke ye-ECHA ebhekisela ngokukodwa kwi-methylene blue, olwaqinisekiswayo. Le nto ikhona kwiirekhodi ze-ECHA ngaphandle kwelo nani linye linxulunyaniswe nayo, ngoko musa ukukopa i-PNEC kwixwebhu lokhuseleko lezinyibilikisi ezixutyiweyo. Njengomzekelo welizwe elinye, i-New Zealand ihlela idayi njenge-Aquatic Chronic 3, H412, eyingozi kwizinto eziphila emanzini neziphumo ezihlala ixesha elide. Lo ngumxholo oluncedo, hayi uhlelo lwaseYurophu.

Isizathu sokuba uncwadi longcoliseko olungumzekelo lungabi yidatha yokuchanabeka

I-methylene blue ixhaphake kakhulu kwiijenali zokunamathela kumphezulu nezokusebenzisa ukukhanya ukukhawulezisa ukusabela, ngenxa yezizathu ezisebenzayo. Ayibizi kakhulu, inombala oqaqambileyo, kulula ukuyilandela ngeendlela ze-spectrophotometry ezisetyenziswa kwizinyibiliko ezixutywe namanzi ezinoxinaniso oluphantsi, inamathela ngamandla kwimiphezulu, yaye inembali yovavanyo olusesikweni nge-ISO 10678 yemiphezulu esebenza nge-photocatalysis. Uncwadi lovavanyo lwe-ISO ngokwalo lulumkisa ukuba ukunamathela kumphezulu, ukusulungeka kwedayi, i-pH, umthombo wokukhanya, nokusasazeka kweemolekyuli kuzisa iimpazamo ezinkulu, kunye nempazamo yokuphindaphindeka kweziphumo phakathi kweelabhoratri esondele kwi-30 pesenti. Ukuba lula kokuyisebenzisa akuthethi ukuba imele iimeko zokwenene.

Amanani aqhelekileyo amanzi amdaka ane dayi akwenza mandundu oku kubhideka. Uphononongo olucatshulwa kakhulu lwamanzi akhutshwa kwiindawo zokudaya lwaxela uxinaniso olupheleleyo lweedayi olumalunga ne-10 ukuya kwi-250 mg/L, kodwa oko kubandakanya iintlobo ezininzi zekhemistri yeedayi yaye akumele nanini kucatshulwe njengoxinaniso lwe-methylene blue. Imilinganiselo yokwenene yale dayi ikhethekileyo iphantsi kakhulu. Uphononongo lwamanzi amdaka oshishino lwamalaphu eMzantsi Afrika lwafumana malunga ne-2.3 mg/L kumanzi angenayo ne-3.2 mg/L kumanzi aphumayo, ngaphambi kokuba ababhali bongeze idayi kwiisampulu ukuze zifike kwi-30 mg/L kwiimvavanyo. Isampulu yamanzi okuhlamba amalaphu e-batik e-Phuket yayiqulethe malunga ne-3.6 mg/L, oku kuqinisekiswa nge-spectrophotometry ne-HPLC. La maxabiso anedijithi enye angaphantsi malunga namaxesha alishumi kune-30 ukuya kwi-50 mg/L edla ngokuba sisiqalo kumaphepha ophando lokususa idayi.

Umgaqo wokufunda olu ncwadi ngulo: ipesenti yokususwa exeliweyo ichaza indlela inkqubo esebenza ngayo xa ivavanywa ngento yokulinganisa yaselabhoratri kuxinaniso lokuqala oluchaziweyo. Ukuchanabeka kufuna idatha yeesampulu echaza iintlobo zeekhemikhali ezikhoyo. Izalathiso ezinxulumene neendlela zohlalutyo zichaza indlela yokugcina lo mahluko ucacile kwiziphumo ezixeliweyo.

Unyango lwamanzi: chaza isiphumo esilinganisiweyo ngaphambi kokuba uthi idayi isusiwe

Zintathu iindidi zonyango lwamanzi ezisusa idayi, yaye nganye inendlela yayo eqhelekileyo yokubaxa impumelelo yayo.

Ukunamathela kumphezulu nokubambeka kwizinto eziphilayo okanye ezivela kuzo kususa idayi emanzini kuyise kwinto eqinileyo: ikhabhoni, udongwe, izinto eziphilayo okanye ezivela kuzo, okanye udaka lonyango lwamanzi. Umda kukuba idluliselwa kwenye imo, hayi ukuba iyatshintshwa ngekhemistri. Ngaphandle kokuba into eyibambileyo esetyenzisiweyo itshatyalaliswe okanye ilahlwe ngokukhuselekileyo, idayi isekhona. Kubhaliwe ukuba le nkqubo inokubuyiselwa umva: uphononongo olunye lokuhluzwa nge-ultrafiltration lwafikelela ekuthintelweni phantse okupheleleyo kwedayi ekuqaleni ngenxa yokunamathela kumphezulu, lwaza lwaphinda lwayifumana idayi ngokuthoba i-pH ukuze iyeke ukunamathela. Olunye uvavanyo lwenwebu yokuhluza lwabonisa ukugcinwa kwedayi kusihla ukusuka malunga ne-20 pesenti kuye kufutshane ne-2 pesenti xa iindawo zokunamathela zazizalisekile. Iisampulu zokuqala zazilinganisa into ebamba idayi, hayi inwebu.

I-oxidation itshabalalisa iqela lemolekyuli elenza umbala, kodwa ukulahleka kombala akuthethi ukuguqulwa ngokupheleleyo zibe ziikhompawundi ezingaphiliyo. I-oxidation ye-Fenton yezinyibiliko ze-10 ukuya kwi-30 mg/L yanika ukususwa kwedayi okungaphezu kwe-98 pesenti ngeyure enye kwi-pH 2 ukuya kwi-3, ngoxa imfuno yekhemikhali yeoksijini yehla kuphela malunga ne-81 pesenti. Unyango nge-ozone lwafikelela ekwahlulweni okupheleleyo okubonakalayo ngemizuzu eli-12 kwi-pH 12, kunye nokuncipha kwe-COD okusondele kwi-65 pesenti. Umsantsa phakathi kwaloo manani mabini kulapho kukho khona iikhompawundi eziphakathi ze-Azure neemveliso ze-oxidation engaphelelanga. Ukususwa kombala, ukwahlulwa kwemolekyuli, ukususwa kwe-COD, nokuguqulwa ngokupheleleyo zibe ziikhompawundi ezingaphiliyo ziziphumo ezine ezahlukeneyo yaye akumele zisetyenziswe ngokungathi ziyafana.

Iinwebu zinokuyithintela idayi ngamazinga aphezulu xa amanzi angenayo elawulwa, kuquka imeko enye yaselabhoratri ye-nanofiltration eyafikelela phantse kwi-99.8 pesenti yokususwa kumanzi angenayo ane-100 mg/L. Kodwa zivelisa umjelo wamanzi axinanisiweyo osafuna ukuphathwa, yaye ukusebenza kwazo ekuqaleni kunokuxhomekeka ngokuyinxenye ekunamatheleni kumphezulu. Ukuqinisekiswa kwinqanaba elipheleleyo lokusebenza libango elahlukileyo kwisiphumo esifumaneka xa amanzi angenayo elawulwa.

Kumsebenzi omncinane waselabhoratri nakwiiprojekthi zolingo, oku kunemiphumo ecacileyo ekusebenzeni. Gcina inkunkuma yedayi yahluliwe yaye inelebhile kunokuba ugalele izinyibiliko eziluhlaza ezinoxinaniso oluphantsi kumjelo wamanzi, ucinga ukuba iziko lonyango lwamanzi liya kuyibolisa ngeentsholongwane. Ukubambeka kudaka kunokwenzeka, kodwa ukutshatyalaliswa akuqinisekiswanga. Amanyathelo asebenzayo ezikhongozeli, okwahlula inkunkuma, nawokuyilahla achaziwe kwisikhokelo sokuphatha inkunkuma yaselabhoratri. Imigaqo yombala wamanzi akhutshwayo, efana nomda waseIndiya we-150 PCU wamanzi akhutshwa kushishino lwamalaphu, ilawula umbala obonakalayo, hayi uxinaniso lwe-methylene blue. Ngoko akukho ndlela enye esebenza kuzo zonke iimeko yokuguqula iiyunithi zombala zibe yi-mg/L kumanzi amdaka axutyiweyo.

Isishwankathelo esinyanisekileyo singena kumhlathi omnye. I-methylene blue ibambeka ngamandla kwezinye izinto, yahlulwa kancinci kukukhanya ngaphandle koncedo, ayinasiphumo sovavanyo olusemgangathweni sokubola okubangelwa zizinto eziphilayo esifunyenweyo, iguquka ibe ziintlobo ze-Azure okanye imo engenambala eyenziwe nge-reduction kunokuba inyamalale, yenzakalisa ezinye izinto eziphila emanzini kuxinaniso olungaphantsi kwe-0.1 mg/L ngoxa ezinye zinyamezela amashumi e-mg/L, ivela kumanzi ambalwa akhutshwayo alinganisiweyo kumanqanaba e-mg/L anedijithi enye, yaye kuthiwa isuswe ngokubambeka kwezinye izinto okanye nge-oxidation kuphela xa isiphumo esilinganisiweyo sichazwe ngokuchanekileyo. Yonke enye into yiflaski eyongezwe idayi elinde isampulu evela kwindawo yokwenene.