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

Klorirani spojevi u mišićnom tkivu riba iz istočnog Jadranskog mora: preliminarni podaci o zagađenosti i zdravstvenim rizicima

Levels of 17 polychlorinated biphenyl congeners (PCBs) and seven organochlorine pesticides (OCPs) were measured in the muscle tissue of 18 commercially important fish species from the eastern Adriatic Sea. PCBs [˂LOD-8,866 ng g-1 lipid weight (lw)] accounted for over 66 % of all analysed compounds. Their pattern was dominated by PCB-138 and PCB-153. DDE (14.2-649 ng g-1 lw) was the prevalent DDT isomer in all samples, suggesting no recent DDT input. β-, γ- and α-HCH and HCB were found in less than 50 % of samples. The analysed organic contaminants did not seem to bioaccumulate up the food web (trophic levels 3.0 to 4.5). Our findings show no risk of chronic (non-cancerous) effects on human health.Maseni udjeli 17 poliklorbifenila (PCB) i 7 organoklorovih pesticida (OCP) izmjereni su u mišićnom tkivu 18 komercijalno važnih ribljih vrsta iz istočnog Jadranskog mora. Maseni udjeli PCB-a (˂LOD do 8.866 ng g-1 masti) činili su više od 66 % svih analiziranih spojeva. U njihovu profilu PCB-138 i PCB-153 dominantni su kongeneri. DDE (14,2-649 ng g-1 masti), glavni izomer DDT-a, jedini je detektiran u svim uzorcima. U manje od 50 % analiziranih uzoraka nađeni su β-, γ- i α-HCH te HCB. U rasponu trofičkih razina analiziranih vrsta (3,0-4,5) nije bilo bioakumulacije organskih zagađivala u hranidbenom lancu. Rezultati procjene rizika za ljudsko zdravlje pokazali su da nema rizika od kroničnih (nekancerogenih) utjecaja na ljudsko zdravlje

Razine organoklorovih spojeva u tkivima kratkokljunog običnog dupina, Delphinus delphis, iz sjevernog Jadranskog mora

We analyzed 17 polychlorinated biphenyls (PCBs) and 7 organochlorine pesticides (OCPs) in blubber, liver, muscle, lung, heart and kidney of an adult male short-beaked common dolphin (Delphinus delphis) found dead stranded on the island of Cres (Croatia) in 2004. The PCB profile was dominated by hexachlorobiphenyls (39.4 – 63.2% of ΣPCB), with PCB-153 exhibiting the highest concentrations across all tissues. The pattern of PCB tissue distribution (ÓPCB) showed the highest burdens in blubber > liver > kidney > heart > muscle > lung, which were positively correlated with tissue lipid content (rs = 0.986, p blubber > liver > kidney > lung > heart, with no correlation to tissue lipid content (p > 0.05). Total DDTs were lower than total PCB levels for all tissues, with ΣPCB/ΣDDTs ratios ranging from 1.3 in blubber to 5.9 in muscles. Blubber OC burdens recorded in our specimen were among the highest found in a dolphin in the Mediterranean after the year 2000. This result and the presence of mono-ortho substituted PCBs with dioxin-like toxicity in all our samples may present an additional factor of concern for the conservation of regional dolphin populations.Analizirali smo 17 poliklorbifenila (PCB) i sedam organoklorovih pesticida (OCP) u potkožnom masnom tkivu, jetri, mišiću, plućima, srcu i bubregu odraslog mužjaka kratkokljunog običnog dupina (Delphinus delphis) koj je nađen nasukan na otoku Cresu (Hrvatska) 2004. godine. PCB profilom dominirali su heksaklorobifenili (39.4 – 63.2% ΣPCB), s PCB-153 utvrđenim s najvišim koncentracijama u svim tkivima. Raspodjela PCB-a u tkivima slijedi redoslijed: potkožno masno tkivo > jetra > bubreg > srce > mišić > pluća te pozitivno korelira sa sadržajem masti u pojedinom tkivu (rs = 0.986, p potkožno masno tkivo > jetra > bubreg > pluća > srce te ne pokazuje korelaciju sa sadržajem masti (p > 0.05). U svim su tkivima razine ukupnih DDT-a bile niže od razina ukupnih PCB-a, a omjeri ΣPCB/ΣDDTs u rasponu su od 1.3 u potkožnom masnom tkivu do 5.9 u mišiću. Razine organoklorovih spojeva u analiziranom uzorku potkožnog masnog tkiva među najvišim su nađenim razinama u dupinima u Sredozemnom moru nakon 2000. godine. Taj podatak te prisutnost mono-ortho supstituiranih PCB-a koji pokazuju toksičnost sličnu dioksinima u svim našim uzorcima mogu predstavljati dodatan razlog ugroženosti regionalne populacije dupina

Chemical Methods for Determination of Hydroxylated Metabolites of Polycyclic Aromatic Hydrocarbons and Polychlorinated Biphenyls in Biological Material

U ovome preglednom radu prikazani su postupci analize hidroksiliranih metabolita policikličkih aromatskih ugljikovodika i poliklorbifenila u ljudima i životinjama. Ti metaboliti služe kao biomarkeri izloženosti ljudi i životinja navedenim zagađivalima, no neki od njih i sami posjeduju toksična svojstva. Analiziraju se najčešće u urinu koji je kao uzorak najdostupniji, ali se isto tako mogu analizirati i u ljudskoj, odnosno životinjskoj jetri, žuči i masnom tkivu. Analiza metabolita aromatskih zagađivala važna je zbog određivanja biodostupnosti aromatskih zagađivala, njihove potencijalne toksičnosti u ljudskom organizmu, ali i zbog toksičnosti samih metabolita. Napredak analitičkih metoda omogućio je simultanu analizu velikog broja metabolita u uzorcima. Nove tehnike ekstrakcije i selektivnije i preciznije kvalitativne i kvantitativne analize omogućuju detekciju vrlo niskih koncentracija metabolita. Pri tome dodatnu prednost imaju jednostavne tehnike koje zahtijevaju manje kemikalija i vremena za analizu.This review presents methods for the analysis of hydroxylated metabolites of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in humans and animals. These metabolites serve as biomarkers of human and animal exposure to the mentioned pollutants, but some metabolites also have toxic properties. Most are analysed in urine, which is the most accessible sample, but they can also be analysed in human and animal liver, bile, and adipose tissue. Their analysis is important for assessing bioavailability of aromatic pollutants and their toxicity in human organism, but also the toxicity of metabolites themselves. Advancements in analytical methods have made it possible to analyse multiple metabolites in a sample at the same time. New extraction techniques and more precise and selective qualitative and quantitative analyses can now detect very low metabolite oncentrations. An extra advantage is that these simple techniques require less chemicals and time

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

Introducing of modeling techniques in the research of POPs in breast milk – A pilot study

This study used advanced statistical and machine learning methods to investigate organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in breast milk, assuming that in a complex biological mixture, the pollutants emitted from the same source or with similar properties are statistically interrelated and possibly exhibit non-linear dynamics. The elaborated analyses such as Unmix source apportionment characterized individual source groups, while guided regularized random forest indicated the pollutant dependence on the ortho-chlorine atom attached to the congener's phenyl ring and mother's age. Mutual associations among PCBs were further discussed, but the results implied they were mostly not related to child delivery. PCB congeners −153, −180, −170, −118, −156, −105, and −138 appeared to be compounds of the outmost importance for mutual prediction with reference to their interrelations regarding chemical structure and metabolic processes in the mother's body. Finally, machine learning methods, which provided prediction relative errors lower than 30% and correlation coefficients higher than 0.90, suggested a possible strong non-linear relationship among the pollutants and consequently, the complexity of their pathways in the breast milk

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in Cyprinidae fish: Towards hints of their arrangements using advanced classification methods

To tackle the ever-present global concern regarding human exposure to persistent organic pollutants (POPs) via food products, this study strived to indicate associations between organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in lake-fish tissue depending on the species and sampling season. Apart from the monitoring initiatives recommended in the Global Monitoring Plan for POPs, the study discussed 7 OCPs and 18 PCB congeners determined in three Cyprinidae species (rudd, carp, and Prussian carp) from Vransko Lake (Croatia), which are widely domesticated and reared as food fish across Europe and Asia. We exploit advanced classification algorithms, the Kohonen self-organizing maps (SOM) and Decision Trees (DT), to search for POP patterns typical for the investigated species. As indicated by SOM, some of the dioxin-like and non-dioxin-like PCBs (PCB-28, PCB-74, PCB-52, PCB-101, PCB-105, PCB-114, PCB-118, PCB-156 and PCB-157), alpha-HCH and beta-HCH caused dissimilarities among fish species, but regardless of their weight and length. To support these suggestions, DT analysis sequenced the fish species and seasons based on the concentration of heavier congeners. The presented assumptions indicated that the supplemental application of SOM and DT offers advantageous features over the usually rough interpretation of POPs pattern and over the single use of the methods

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in Cyprinidae fish: Towards hints of their arrangements using advanced classification methods

To tackle the ever-present global concern regarding human exposure to persistent organic pollutants (POPs) via food products, this study strived to indicate associations between organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in lake-fish tissue depending on the species and sampling season. Apart from the monitoring initiatives recommended in the Global Monitoring Plan for POPs, the study discussed 7 OCPs and 18 PCB congeners determined in three Cyprinidae species (rudd, carp, and Prussian carp) from Vransko Lake (Croatia), which are widely domesticated and reared as food fish across Europe and Asia. We exploit advanced classification algorithms, the Kohonen self-organizing maps (SOM) and Decision Trees (DT), to search for POP patterns typical for the investigated species. As indicated by SOM, some of the dioxin-like and non-dioxin-like PCBs (PCB-28, PCB-74, PCB-52, PCB-101, PCB-105, PCB-114, PCB-118, PCB-156 and PCB-157), alpha-HCH and beta-HCH caused dissimilarities among fish species, but regardless of their weight and length. To support these suggestions, DT analysis sequenced the fish species and seasons based on the concentration of heavier congeners. The presented assumptions indicated that the supplemental application of SOM and DT offers advantageous features over the usually rough interpretation of POPs pattern and over the single use of the methods