Trace analysis of persistent organochlorine compounds in soil and atmospheric particles

Razrađeni su postupci mikrovalne ili ultrazvučne ekstrakcije za multirezidualnu analizu tragova organoklorovih (OC) pesticida i specifičnih kongenera polikloriranih bifenila u tlu (35 spojeva) i u frakciji lebdećih čestica PM2,5 u zraku (27 spojeva). Otapalo za ekstrakciju bila je smjesa (n-heksan, aceton)=1:1. Pročišćeni ekstrakti analizirani su plinskom kromatografijom uz detekciju spojeva detektorom zahvata elektrona i spektrometrijom masa. Istražen je utjecaj sastojaka matrice tla na djelotvornost dvaju različitih postupaka ekstrakcije i selektivnost i osjetljivost odziva detektora. Mikrovalna ekstrakcija primijenjena je za analizu OC spojeva u tlima i jezerskim sedimentima skupljenim na području Nacionalnog parka Plitvička jezera te tlima skupljenim na području grada Varaždina, a ultrazvučna za analizu istih zagađivala u lebdećim česticama PM2,5 skupljenim u Zagrebu. Maseni udjeli OC zagađivala u tlu i sedimentima (ng kg-1 do g kg-1) kao i njihove masene koncentracije u česticama u zraku (pg m3) bili su na razini globalnog onečišćenja okoliša. U uzorcima tla i sedimenata najčešće je detektiran p,p'-DDE, a u česticama PM2,5 u zraku -heksaklorcikloheksan. Omjeri p,p'-DDE/p,p'-DDT u varaždinskim tlima i u lebdećim česticama u zraku upućuju na stalni unos tragova p,p'-DDT-a u okoliš. Masene koncentracije OC zagađivala u česticama PM2,5 u zraku bile su 2010. godine znatno niže od onih izmjerenih na istoj lokaciji u razdoblju od 2000. do 2003. godine.Abstract Microwave-assisted or ultrasound-assisted extraction procedures were developed for multiresidue trace analysis of organochlorine (OC) pesticides and specific polychlorinated biphenyl congeners in soil (35 compounds) and atmospheric particles PM2.5 (27 compounds). The extraction solvent was the mixture (n-hexane, acetone)=1:1. Purified extracts were analysed using gas chromatography with electron capture and mass spectrometric detection. The influence of soil matrix components on the efficiency of two different extraction procedures and on the selectivity and sensitivity of detector response was investigated. The microwave-assisted extraction was applied for the analysis of OC compounds in soils and lake sediments collected in the area of Plitvice Lakes National Park and in soils collected in the city of Varaždin, while the ultrasonic extraction was used for analyses of these pollutants in PM2.5 atmospheric particles collected in Zagreb. Mass fractions of OC pollutants in soils and sediments (ng kg-1 to g kg-1) as well as their mass concentrations in particles in air (pg m3) were at levels of global environmental pollution. The most frequently detected OC pollutant in soils and sediments was p,p'-DDE, and in PM2,5 particles in air -hexachlorocyclohexane. The p,p-DDE/p,p-DDT in Varaždin soils and in atmospheric particles indicated a constant input of p,p-DDT traces in the environment. Mass concentrations of OC pollutants in PM2.5 particles in air were considerably lower in 2010 than those measured at the same location in the 2000 to 2003 period

Trace analysis of persistent organochlorine compounds in soil and atmospheric particles

Razrađeni su postupci mikrovalne ili ultrazvučne ekstrakcije za multirezidualnu analizu tragova organoklorovih (OC) pesticida i specifičnih kongenera polikloriranih bifenila u tlu (35 spojeva) i u frakciji lebdećih čestica PM2,5 u zraku (27 spojeva). Otapalo za ekstrakciju bila je smjesa (n-heksan, aceton)=1:1. Pročišćeni ekstrakti analizirani su plinskom kromatografijom uz detekciju spojeva detektorom zahvata elektrona i spektrometrijom masa. Istražen je utjecaj sastojaka matrice tla na djelotvornost dvaju različitih postupaka ekstrakcije i selektivnost i osjetljivost odziva detektora. Mikrovalna ekstrakcija primijenjena je za analizu OC spojeva u tlima i jezerskim sedimentima skupljenim na području Nacionalnog parka Plitvička jezera te tlima skupljenim na području grada Varaždina, a ultrazvučna za analizu istih zagađivala u lebdećim česticama PM2,5 skupljenim u Zagrebu. Maseni udjeli OC zagađivala u tlu i sedimentima (ng kg-1 do g kg-1) kao i njihove masene koncentracije u česticama u zraku (pg m3) bili su na razini globalnog onečišćenja okoliša. U uzorcima tla i sedimenata najčešće je detektiran p,p'-DDE, a u česticama PM2,5 u zraku -heksaklorcikloheksan. Omjeri p,p'-DDE/p,p'-DDT u varaždinskim tlima i u lebdećim česticama u zraku upućuju na stalni unos tragova p,p'-DDT-a u okoliš. Masene koncentracije OC zagađivala u česticama PM2,5 u zraku bile su 2010. godine znatno niže od onih izmjerenih na istoj lokaciji u razdoblju od 2000. do 2003. godine.Abstract Microwave-assisted or ultrasound-assisted extraction procedures were developed for multiresidue trace analysis of organochlorine (OC) pesticides and specific polychlorinated biphenyl congeners in soil (35 compounds) and atmospheric particles PM2.5 (27 compounds). The extraction solvent was the mixture (n-hexane, acetone)=1:1. Purified extracts were analysed using gas chromatography with electron capture and mass spectrometric detection. The influence of soil matrix components on the efficiency of two different extraction procedures and on the selectivity and sensitivity of detector response was investigated. The microwave-assisted extraction was applied for the analysis of OC compounds in soils and lake sediments collected in the area of Plitvice Lakes National Park and in soils collected in the city of Varaždin, while the ultrasonic extraction was used for analyses of these pollutants in PM2.5 atmospheric particles collected in Zagreb. Mass fractions of OC pollutants in soils and sediments (ng kg-1 to g kg-1) as well as their mass concentrations in particles in air (pg m3) were at levels of global environmental pollution. The most frequently detected OC pollutant in soils and sediments was p,p'-DDE, and in PM2,5 particles in air -hexachlorocyclohexane. The p,p-DDE/p,p-DDT in Varaždin soils and in atmospheric particles indicated a constant input of p,p-DDT traces in the environment. Mass concentrations of OC pollutants in PM2.5 particles in air were considerably lower in 2010 than those measured at the same location in the 2000 to 2003 period

Trace analysis of persistent organochlorine compounds in soil and atmospheric particles

Razrađeni su postupci mikrovalne ili ultrazvučne ekstrakcije za multirezidualnu analizu tragova organoklorovih (OC) pesticida i specifičnih kongenera polikloriranih bifenila u tlu (35 spojeva) i u frakciji lebdećih čestica PM2,5 u zraku (27 spojeva). Otapalo za ekstrakciju bila je smjesa (n-heksan, aceton)=1:1. Pročišćeni ekstrakti analizirani su plinskom kromatografijom uz detekciju spojeva detektorom zahvata elektrona i spektrometrijom masa. Istražen je utjecaj sastojaka matrice tla na djelotvornost dvaju različitih postupaka ekstrakcije i selektivnost i osjetljivost odziva detektora. Mikrovalna ekstrakcija primijenjena je za analizu OC spojeva u tlima i jezerskim sedimentima skupljenim na području Nacionalnog parka Plitvička jezera te tlima skupljenim na području grada Varaždina, a ultrazvučna za analizu istih zagađivala u lebdećim česticama PM2,5 skupljenim u Zagrebu. Maseni udjeli OC zagađivala u tlu i sedimentima (ng kg-1 do g kg-1) kao i njihove masene koncentracije u česticama u zraku (pg m3) bili su na razini globalnog onečišćenja okoliša. U uzorcima tla i sedimenata najčešće je detektiran p,p'-DDE, a u česticama PM2,5 u zraku -heksaklorcikloheksan. Omjeri p,p'-DDE/p,p'-DDT u varaždinskim tlima i u lebdećim česticama u zraku upućuju na stalni unos tragova p,p'-DDT-a u okoliš. Masene koncentracije OC zagađivala u česticama PM2,5 u zraku bile su 2010. godine znatno niže od onih izmjerenih na istoj lokaciji u razdoblju od 2000. do 2003. godine.Abstract Microwave-assisted or ultrasound-assisted extraction procedures were developed for multiresidue trace analysis of organochlorine (OC) pesticides and specific polychlorinated biphenyl congeners in soil (35 compounds) and atmospheric particles PM2.5 (27 compounds). The extraction solvent was the mixture (n-hexane, acetone)=1:1. Purified extracts were analysed using gas chromatography with electron capture and mass spectrometric detection. The influence of soil matrix components on the efficiency of two different extraction procedures and on the selectivity and sensitivity of detector response was investigated. The microwave-assisted extraction was applied for the analysis of OC compounds in soils and lake sediments collected in the area of Plitvice Lakes National Park and in soils collected in the city of Varaždin, while the ultrasonic extraction was used for analyses of these pollutants in PM2.5 atmospheric particles collected in Zagreb. Mass fractions of OC pollutants in soils and sediments (ng kg-1 to g kg-1) as well as their mass concentrations in particles in air (pg m3) were at levels of global environmental pollution. The most frequently detected OC pollutant in soils and sediments was p,p'-DDE, and in PM2,5 particles in air -hexachlorocyclohexane. The p,p-DDE/p,p-DDT in Varaždin soils and in atmospheric particles indicated a constant input of p,p-DDT traces in the environment. Mass concentrations of OC pollutants in PM2.5 particles in air were considerably lower in 2010 than those measured at the same location in the 2000 to 2003 period

Analitika bromiranih usporivača gorenja u vodenom okolišu – pregledni rad

The most common and consequently analysed brominated flame retardants (BFRs) are polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), tetrabromobisphenol S (TBBPS), and hexabromocyclododecane (HBCD). As these persistent organic pollutants are widespread in the environment and have a number of harmful effects on human health, the production and use of most has been banned for several years. The aquatic environment is polluted by these compounds through their deposition from the atmosphere, sewage sludge, wastewater treatment plants, and landfills, and higher levels are found in areas with developed industry and agriculture and near landfills. Each compound also seems to show preference for specific compartments of the aquatic environment, i.e. water, sediment, or aquatic organisms, according to their physicochemical properties. The aim of this review was to take a closer look at the analysis of BFRs, as without reliable analysis we would not be able to determine their levels and distribution across the aquatic compartments and assess human exposure and health risks. Particularly worrying are the health risks associated with PBDEs in fish, whose levels generally exceed the permitted values.Najčešće korišteni, a posljedično i analizirani bromirani usporivači gorenja su polibromirani bifenili (PBB), polibromiranidifenil eteri (PBDE), tetrabromobisfenol A (TBBPA), tetrabromobisfenol S (TBBPS) i heksabromociklododekan (HBCD). Navedeni spojevi smatraju se postojanim organskim zagađivalima, a s obzirom na to da su široko rasprostranjeni u okolišu i dokazano imaju niz negativnih štetnih učinaka na ljudsko zdravlje, proizvodnja i upotreba većine njih strogo je zabranjena. Vodeni je okoliš izložen ovim spojevima njihovim taloženjem iz atmosfere, mulja otpadnih voda, postrojenja za pročišćavanje otpadnih voda i ispiranjem odlagališta otpada, a ovisno o fizikalno-kemijskim svojstvima pojedinog spoja prisutan je u većim koncentracijama/udjelima u određenom dijelu vodenog okoliša. Više razine pronalaze se u područjima s razvijenom industrijom i poljoprivredom te u blizini odlagališta otpada. Cilj ovoga rada bio je detaljno i sažeto objasniti analitiku navedenih spojeva u vodenom okolišu – vodi, sedimentu i vodenim organizmima. Analitika spojeva bromiranih usporivača gorenja iznimno je važna kako bi se pouzdano mogle odrediti njihove razine i raspodjela u vodenom okolišu te na temelju dobivenih podataka procijeniti izloženost ljudi ovim spojevima. Posebno je zabrinjavajuće što zbroj masenih udjela spojeva PBDE u ribi uglavnom prelazi dopuštene vrijednosti

Dinamika disipacije terbutilazina u tlu tijekom vegetacije kukuruza

Ever since terbuthylazine (TBA) replaced atrazine in herbicide crop treatment, its much greater persistence has raised considerable environmental concern. The aim of our field experiment was to establish the dissipation dynamics of TBA and its degradation product desethylterbuthylazine (DET) in soil over five months of maize growth. We applied TBA as part of pre-emergent treatment in the regular and double-the-regular amounts. Soil samples were collected periodically at the following depths: 0-10 cm, 10-20 cm, 20-30 cm, and 30-50 cm. For TBA and DET soil residue analysis we used microwave-assisted extraction with methanol, followed by HPLC-UV/DAD. Regardless of the application rate, more than 80 % of the applied TBA dissipated from the first 50 cm of soil in the two months after herbicide application and 120 mm of rainfall. Three months later (at maize harvest), less than 4 % of total TBA remained in the soil, mostly in the top 20 cm rich with organic carbon on which TBA is likelier to adsorb. The loss of TBA from soil coincided with the rise in DET, especially the top soil layers, during the periods of low rainfall and highest soil temperatures. This points to biodegradation as the main route of TBA dissipation in humic soils. The applied amount had no significant effect on TBA dissipation in the top (humic) layers, but in the layers with less than 1 % of organic carbon, it was higher when the double-the-regular dose was applied.Terensko istraživanje dinamike disipacije herbicida terbutilazina (TBA) i njegova razgradnog produkta deetilterbutilazina (DET) u tlu provodilo se tijekom pet mjeseci proizvodnje kukuruza. Terbutilazin je primijenjen kao zemljišni herbicid u propisanoj dozi i u dvostruko višoj dozi od propisane. Uzorci tla periodično su skupljani pri dubinama 0-10 cm, 10-20 cm, 20-30 cm i 30-50 cm. Ostaci herbicida u tlu ekstrahirani su metanolom uz primjenu mikrovalova te analizirani HPLC-UV/DAD sustavom. Bez obzira na dozu, više od 80 % TBA rasipalo se iz prvih 50 centimetara tla dva mjeseca nakon primjene herbicida (nakon 120 mm oborina). Tri mjeseca poslije (nakon žetve kukuruza) u tlu je ostalo manje od 4 % primijenjenog TBA, uglavnom u površinskim humusnim slojevima gdje se može očekivati adsorpcija TBA na organski ugljik. Gubitak TBA iz tla praćen je porastom masenih udjela DET-a, osobito u razdoblju rijetkih oborina i najviših prosječnih temperatura tla. Najviše razine DET-a određene su u humusnim slojevima tla. Postojanost TBA u tlu značajno negativno korelira sa sadržajem humusa, što upućuje na biorazgradnju kao glavni put disipacije TBA u humusnom tlu. Doza herbicida ne utječe značajnije na brzinu disipacije u humusnom sloju tla, ali u tlu s manje od 1 % organskog ugljika može se očekivati brža disipacija TBA pri dvostrukoj nego pri propisanoj dozi

Dinamika disipacije terbutilazina u tlu tijekom vegetacije kukuruza

Ever since terbuthylazine (TBA) replaced atrazine in herbicide crop treatment, its much greater persistence has raised considerable environmental concern. The aim of our field experiment was to establish the dissipation dynamics of TBA and its degradation product desethylterbuthylazine (DET) in soil over five months of maize growth. We applied TBA as part of pre-emergent treatment in the regular and double-the-regular amounts. Soil samples were collected periodically at the following depths: 0-10 cm, 10-20 cm, 20-30 cm, and 30-50 cm. For TBA and DET soil residue analysis we used microwave-assisted extraction with methanol, followed by HPLC-UV/DAD. Regardless of the application rate, more than 80 % of the applied TBA dissipated from the first 50 cm of soil in the two months after herbicide application and 120 mm of rainfall. Three months later (at maize harvest), less than 4 % of total TBA remained in the soil, mostly in the top 20 cm rich with organic carbon on which TBA is likelier to adsorb. The loss of TBA from soil coincided with the rise in DET, especially the top soil layers, during the periods of low rainfall and highest soil temperatures. This points to biodegradation as the main route of TBA dissipation in humic soils. The applied amount had no significant effect on TBA dissipation in the top (humic) layers, but in the layers with less than 1 % of organic carbon, it was higher when the double-the-regular dose was applied.Terensko istraživanje dinamike disipacije herbicida terbutilazina (TBA) i njegova razgradnog produkta deetilterbutilazina (DET) u tlu provodilo se tijekom pet mjeseci proizvodnje kukuruza. Terbutilazin je primijenjen kao zemljišni herbicid u propisanoj dozi i u dvostruko višoj dozi od propisane. Uzorci tla periodično su skupljani pri dubinama 0-10 cm, 10-20 cm, 20-30 cm i 30-50 cm. Ostaci herbicida u tlu ekstrahirani su metanolom uz primjenu mikrovalova te analizirani HPLC-UV/DAD sustavom. Bez obzira na dozu, više od 80 % TBA rasipalo se iz prvih 50 centimetara tla dva mjeseca nakon primjene herbicida (nakon 120 mm oborina). Tri mjeseca poslije (nakon žetve kukuruza) u tlu je ostalo manje od 4 % primijenjenog TBA, uglavnom u površinskim humusnim slojevima gdje se može očekivati adsorpcija TBA na organski ugljik. Gubitak TBA iz tla praćen je porastom masenih udjela DET-a, osobito u razdoblju rijetkih oborina i najviših prosječnih temperatura tla. Najviše razine DET-a određene su u humusnim slojevima tla. Postojanost TBA u tlu značajno negativno korelira sa sadržajem humusa, što upućuje na biorazgradnju kao glavni put disipacije TBA u humusnom tlu. Doza herbicida ne utječe značajnije na brzinu disipacije u humusnom sloju tla, ali u tlu s manje od 1 % organskog ugljika može se očekivati brža disipacija TBA pri dvostrukoj nego pri propisanoj dozi

Organochlorine Pesticides and Polychlorinated Biphenyls in Atmospheric Particles Collected in Zagreb, Croatia

We studied the occurrence and levels of hexachlorobenzene, α-, β-, and γ-hexachlorocyclo-hexane, 4,4\u27-DDT, 4,4\u27-DDE, 4,4\u27-DDD, and 17 PCBs (six indicator and eleven other toxicologically significant congeners) in PM10 and/or PM2.5 particle fractions collected between 2000 and 2003 and in 2010 at a site in the northern residential part of Zagreb, Croatia. Twenty-four-hour particle samples were collected on glass or quartz microfibre filters from approximately 100 m3 of ambient air per filter. Filters with particles collected over seven consecutive days were combined for ultrasonic extraction with 1:1 acetone:n-hexane mixture followed by capillary gas chromatography with electron capture detection. In the monitored periods, the mass concentrations of organochlorine compounds in atmospheric particles were characteristic of global environmental pollution and showed a decreasing trend. Local input was observed only for γ-hexachlorocyclohexane. There were no pronounced seasonal variations in the mass fraction levels of any pesticide or PCB in airborne particles. A decreasing trend in the mass concentrations of some compounds with higher air temperatures was mostly related to the lower particle concentrations in warmer seasons and, consequently, to less particle-bound organochlorine compounds in the atmosphere

Sezonska raspodjela različitih klasa pesticida u površinskim vodama sjeverozapadne Hrvatske

As part of our OPENTOX project, we evaluated the incidence and mass concentrations of multiclass pesticide residues in 23 river/stream water samples collected in urban and agricultural areas of northwest Croatia at various points of the pesticide application season in 2015. The study included 16 compounds of five herbicide classes and seven compounds of three insecticide classes. Pesticide residues were accumulated from water by solid-phase extraction and analysed using high performance liquid chromatography with UV-diode array detection and/or gas chromatography-mass spectrometry. Herbicide residues were more common than the insecticide ones, and, as expected, they peaked in the middle of the application season. Metolachlor showed the highest concentrations and was found in 91 % of all samples, followed by terbuthylazine, found in 70 % of the samples. The highest total mass concentration of detected pesticides was measured in the water samples of the Krapina (3992 ng/L) and Sutla (3455 ng/L) collected in rural areas with intensive agriculture. Our findings strongly speak in favour of continued monitoring of surface waters and possibly extending the list of priority water pollutants.U sklopu našega projekta OPENTOX odredili smo masene koncentracije ostataka pesticida i njihovu učestalost u 23 uzorka vode rijeka/potoka u gradskim i ruralnim dijelovima sjeverozapadne Hrvatske, prikupljenih 2015. tijekom sezone njihove primjene. Istraživanje je obuhvatilo 16 spojeva iz pet različitih klasa herbicida i sedam spojeva iz triju klasa insekticida. Ostaci pesticida akumulirani su iz vode postupkom ekstrakcije na čvrstoj fazi i analizirani tekućinskom kromatografijom visoke djelotvornosti uz UV-detektor s nizom dioda ili vezanim sustavom plinske kromatografije I spektrometrije masa. Češće su detektirani ostatci herbicida nego insekticida, a najviše su koncentracije bile sredinom sezone njihove primjene. Metolaklor je određen u najvišoj koncentraciji i u najvećem broju uzoraka (91 %), a slijedio ga je terbutilazin, koji je nađen u 70 % uzoraka. Najviša ukupna razina određivanih pesticida bila je u uzorcima rijeka Krapine (3992 ng/L) i Sutle (3455 ng/L), koji su bili prikupljeni u ruralnom području s intenzivnom poljoprivredom. Rezultati našega istraživanja govore u prilog potrebi ne samo za kontinuiranim monitoringom pesticida u površinskim vodama nego i za proširenjem liste prioritetnih zagađivala

PBDEs Found in House Dust Impact Human Lung Epithelial Cell Homeostasis

The toxicity of eight polybrominated diphenyl ethers (PBDEs) congeners detected in environmental and biological samples (BDE-28, -47, -99, -100, -153, -154, -183, and -209) was evaluated on the epithelial lung cells. Exposure to these PBDEs increased membrane disruption and a release of lactate dehydrogenase, accompanied by oxidative stress in cells through the formation of reactive oxygen species (ROS) and a decrease in mitochondrial membrane potential. Interestingly, some of the tested PBDEs increased apoptotic markers as well. For several congeners, the observed toxicity was time dependent, meaning that even smaller concentrations of these compounds will have negative effects over time. Such time-dependent toxicity was also confirmed for cell treatment with a real house dust sample extract. This could be indicative with regard to the constant exposure to a mixture of PBDE congeners through different pathways in the organism and thereby presenting a risk for human health. As such, our findings point to the importance of further studies on the negative effects of PBDEs to understand their mechanism of action in detail