Procjena zdravstvenog rizika izloženosti toksičnim elementima u mesu i mesnim proizvodima iz Hrvatske

The aim of this study was to measure the concentrations of arsenic (As), cadmium (Cd), lead (Pb), aluminium (Al), chromium (Cr) and nickel (Ni) in meat (pork and beef neck) and meat products (meat with beans, breakfast meat, chicken pâté, ham, and pork sausage) purchased from supermarkets in several Croatian cities. Element concentrations were analysed using inductively coupled plasma mass spectrometry (ICP-MS). Mean element concentrations in meat and meat products were measured in the ranges (μg/kg): Al 523-19,179, As 2.25-5.63, Cd 2.02-2.86, Cr 20.8-132.6, Ni 4.78-166.9, Pb, 3.53-7.49. The highest mean concentrations of elements were found in: Al in chicken pâté; As and Cd in ham; Cr and Ni in meat with beans; Pb in pork sausage. All measured Cd and Pb levels were below the European Commission limits of 50 and 100 μg/kg, respectively, and there were no significant differences in these elements between products. Significant differences in the content of Al, As, Cr and Ni were determined between meat and meat products. An estimation of the dietary daily (EDI) and weekly (EWI) intakes of elements associated with the consumption of meat and meat products were calculated. Measured element concentrations in meat and meat products contributed to the provisional tolerable weekly intake level (PTWI) and tolerable weekly intake level (TWI) in the ranges (%): 1.13-43.5 (Al); 0.33-0.87 (As); 0.32- 0.68 (Pb); 2-2.4 (Cd), and to the permitted daily exposure (PDE) values in the ranges (%): 0.03-0.17 (Cr); 0.003-0.18 (Ni). Results of comparison with the toxicological reference values suggest no concern with regard to exposure to the analysed elements for consumers who often consume these meats and meat products. The exception is Cr content, which may pose a problem given the values set by the national legislation. Lower concentrations of As, Al, Cd, Cr, Ni and Pb in meat and meat products were determined in this study in comparison with the available literature data from other countries.Cilj ovog istraživanja bio je određivanje koncentracija toksičnih metala arsena (As), kadmija (Cd) i olova (Pb), kao i aluminija (Al), kroma (Cr) i nikla (Ni) u mesu (svinjska i goveđa vratina) i mesnim proizvodima (meso s grahom, mesni doručak, pileća pašteta, šunka i svinjska kobasica) nabavljenih u trgovačkim lancima različitih hrvatskih gradova. Koncentracije elemenata analizirane su primjenom masene spektrometrije induktivno spregnute plazme (ICP-MS). Srednje koncentracije elemenata u mesu i mesnim proizvodima mjerene su u rasponu (μg/kg): Al 523-19179, As 2,25-5,63, Cd 2,02- 2,86, Cr 20,8-132,6, Ni 4,78-166,9, Pb 3,53- 7,49. Najveće srednje koncentracije elemenata određene su u: Al u pilećoj pašteti, As i Cd u šunki, Cr i Ni u mesu s grahom, Pb u svinjskoj kobasici. Sve izmjerene koncentracije Cd i Pb bile su ispod granica Europske komisije od 50 i 100 μg/kg. Ustvrđene su statistički značajne razlike u sadržaju Al, As, Cr i Ni između mesa i mesnih proizvoda. Nije bilo značajnih razlika u koncentracijama Cd i Pb. Izračunata je dnevna (EDI) i tjedna (EWI) količina unesenih elemenata povezanih s potrošnjom mesa i proizvoda. Određene koncentracije Al, As, Pb i Cd u mesu i mesnim proizvodima pridonijele su privremenim podnošljivim tjednim nivoima unosa (PTWI) i podnošljivom tjednom unosu (TWI) u rasponima (%): 1,13-43,5; 0,33-0,87; 0,32-0,68; 2-2,4. Također, koncentracije Cr i Ni izmjerene u mesu i mesnim proizvodima pridonijele su dopuštenim dnevnim vrijednostima izlaganja (PDE) u rasponima (%): 0,03- 0,17 i 0,003-0,18. Rezultati usporedbe s toksikološkim referentnim vrijednostima ne ukazuju na zabrinutost s obzirom na izloženost analiziranim elementima za potrošače koji često konzumiraju istražene vrste mesa i mesnih proizvoda. Izuzetak je sadržaj Cr, što može predstavljati problem s obzirom na vrijednosti ustvrđene nacionalnim zakonodavstvom. U ovom istraživanju ustvrđene su uglavnom niže koncentracije As, Al, Cd, Cr, Ni i Pb u mesu i mesnim proizvodima u usporedbi s dostupnim literaturnim podatcima u mesu i proizvodima iz drugih zemalja

Insecticide fipronil in poultry products in the European Union

Fipronil je insekticid širokog spektra djelovanja koji se ubraja u skupinu fenilpirazola. Prvi je insekticid koji je djelovao ciljajući GABA (gama-aminomaslačnu kiselinu) receptor i imao povoljnu selektivnu toksičnost prema insektima, ali ne i sisavcima. U skladu s uredbom (EZ) br. 1107/2009. fipronil nije odobren u sredstvima za zaštitu bilja te je zabranjeno tretiranje životinja namijenjenih za prehranu ljudi u Europskoj uniji (EU). Najveća dopuštena količina (NDK) fipronila ustvrđena je prema Uredbi 396/2005. o maksimalnim razinama ostataka pesticida u i na hrani i hrani za životinje biljnog i životinjskog podrijetla te za jaja i meso peradi iznosi 0,005 mg/kg. Svjetska zdravstvena organizacija (WHO) klasificirala je fipronil kao umjereno opasan pesticid II klase. Konzumiranje malih količina fipronila izaziva mučninu, glavobolju, povraćanje, bol u želucu, slabost i vrtoglavicu. Nakon apsorpcije u ljudi distribuira se u tkiva i oslobađa aktivne metabolite koji se nakupljaju uglavnom u masnom tkivu. Eksperimenti na miševima pokazali su da produljena izloženost visokim dozama fipronila prouzroči rak štitnjače u mužjaka i ženki. Pojava fipronila u jajima u EU zabilježena je 2016. godine u Belgiji. Kao posljedica ustvrđene zlouporabe fipronila na farmama pilića, države članice EU i Europska komisija dogovorile su provedbu ad-hoc monitoringa na ostatke insekticida fipronila i drugih akaricida u jajima i mesu peradi. Europska agencija za sigurnost hrane (EFSA) objavila je izvješće o rezultatima monitoringa te su u ukupnoj količini od 5439 uzoraka jaja i mesa peradi u zemljama članicama EU i Islandu u 742 uzorka (13,6 %) ustvrđene količine veće od zakonski dopuštenih. Većina nesukladnih rezultata odnosila se na fipronil u uzorcima kokošjih jaja i masnog tkiva kokoši nesilica. U uzorcima iz Republike Hrvatske nisu ustvrđeni nesukladni rezultati. Uzorci koji su prekoračili zakonsko ograničenje bili su podrijetlom iz Nizozemske, Italije, Njemačke, Poljske, Mađarske, Francuske, Slovenije i Grčke. Članice EU su u kontroli proizvoda koji se upućuju na tržište EU nesukladne rezultate fipronila prijavljivale u razdoblju 2017.-2019. putem centralnog sustava brzog uzbunjivanja za hranu i hranu za životinje - RASFF. Ukupno je prijavljeno 128 različitih proizvoda s nesukladnim koncentracijama fipronila, a najviše se obavijesti odnosilo na jaja i proizvode od jaja. Pri tome je u okviru poduzetih mjera za čak 45 prijava provedeno povlačenje kontaminiranih jaja s tržišta, obavljeno je po 9 zapljena i 9 službenih pritvora. Na temelju ustvrđenih nesukladnih nalaza fipronila Europska komisija je prema Provedbenoj Uredbi Komisije (EU) 2019/533 uvrstila njegovu kontrolu u okviru koordiniranog višegodišnjeg programa kontrole EU za razdoblje 2020.-2022.Fipronil is a broad-spectrum insecticide that belongs to the phenylpyrazole group. It is an insecticide that acts by targeting the GABA (gamma aminobutyric acid) receptor and has favourable selective toxicity to insects rather than mammals. Pursuant to Regulation (EC) No. 1107/2009, fipronil is not authorized in plant protection products and it is forbidden to treat animals intended for human consumption in the European Union (EU). The maximum permitted residue level (MRL) of fipronil is 0.005 mg/ kg for eggs and poultry, as established under Regulation 396/2005 on maximum levels of pesticide residues in and on food and feed of plant and animal origin. The World Health Organization (WHO) has classified fipronil as a mildly dangerous class II pesticide. Consuming small amounts of fipronil causes nausea, headache, vomiting, stomach pain, weakness and dizziness. After absorption in humans, it is distributed into tissues and releases active metabolites that accumulate mainly in adipose tissue. Experiments in mice have shown that prolonged exposure to high doses of fipronil causes thyroid cancer in males and females. The occurrence of fipronil in eggs in the EU was reported in Belgium in 2016. As a consequence of the identified misuse of fipronil found on chicken farms, EU Member States and the European Commission have agreed to carry out ad-hoc monitoring of fipronil insecticides and other acaricides in eggs and poultry meat. In a monitoring report published by the European Food Safety Authority (EFSA), 742 samples (13.6%) of a total of 5439 eggs and poultry samples in EU Member States and Iceland exceeded the legal limits. Most inconsistent results were related to fipronil in chicken eggs and fat of laying hens. No non-compliant results were found in samples from the Republic of Croatia. Samples exceeding the legal limit originated from the Netherlands, Italy, Germany, Poland, Hungary, France, Slovenia and Greece. EU Member States reported non-compliant fipronil results in the control of products marketed in the EU during 2017-2019 via the Central Rapid Alert System for Food and Feed (RASFF). In total, 128 different products with non-compliant fipronil concentrations were reported, with the most reports regarding eggs and egg products. In the framework of the measures taken, as many as 45 complaints were filed to withdraw contaminated eggs from the market, and nine confiscations and nine official detentions were carried out. Based on the identified non-compliant findings of fipronil, the European Commission has listed its control under Commission Coordinated Implementing Regulation (EU) 2019/533 under the coordinated multi-annual EU control program for the period 2020-2022

Content of cadmium, mercury and lead in bovine and porcine kidney tissue

U radu su prikazani rezultati istraživanja teških metala kadmija (Cd), žive (Hg) i olova (Pb) u bubrežnom tkivu 78 goveda i 45 svinja iz ruralnih područja Republike Hrvatske uzorkovanih tijekom 2009. godine. Sadržaj Cd i Pb je određen metodom atomske apsorpcijske spektrometrije primjenom gratne tehnike, a Hg direktnim spaljivanjem na živinom analizatoru. Količine Cd, Hg i Pb određene u bubrežnom tkivu goveda bile su znatno više u odnosu na količine utvrđene u svinja. Dobivene vrijednosti Cd i Pb podudaraju se sa re- zultatima u goveda i svinja, dok su utvrđene količine Hg u obje vrste životinja niže od količina utvrđenih u ruralnim područjima drugih zemalja Europske Zajednice. U 13 % uzoraka bubrega goveda utvrđene količine Cd su više od najviše dopuštene količine od 1 mg/kg, dok su u svega 1,15 % bubrežnog tkiva goveda utvrđene količine Pb bile više od najviše dopuštene količine od 0,5 mg/kg. U bubrezima svinja nisu utvrđene količine iznad najviših dopuštenih količina. Najviše dopuštene količine Hg nisu određene legislativom Europske Zajednice odnosno Republike Hrvatske te su dobiveni rezultati uspoređeni sa literaturnim vrijednostima. Samo u 1,15 % uzoraka bubrega goveda količine Hg su prelazile 0,03 mg/kg, dok u svinja nije utvrđen niti jedan takav slučaj. Dobiveni rezultati potvrđuju potrebu kontrole količina Cd, Hg i Pb u bubrežnom tkivu goveda na liniji klanja. Istovremeno bubrežno tkivo svinja je pogodno za konzumaciju široke populacije jer su utvrđene količine Cd i Pb ispod najviših dopuštenih količina.The paper presents the results of the study of heavy metals: cadmium (Cd), mercury (Hg) and lead (Pb) in kidney tissue of 78 cattle and 45 pigs from rural regions of Croatia, sampled in 2009. Cd and Pb levels were determined by atomic absorption spectrometry by application of graphite technique, and Hg levels by direct burning on a mercury analyser. Cd, Hg and Pb levels determined in bovine kidney tissue signicantly exceeded the levels established in pigs. The obtained results of Cd and Pb corresponded to the values from rural regions of other EU countries, while Hg levels were lower in comparison to other EU regions. In 13% of bovine kidney samples, Cd levels exceeding the maximum permitted levels (1 mg/kg) were found, while only in 1.15% of bovine kidney tissue, Pb levels exceeded the maximum permitted ones (0.5 mg/kg). Levels exceeding the maximum permitted quantity were not found in porcine kidneys. Maximum permitted Hg levels are not set forth in EU or Croatian legislation; thus the results were compared with reference values. In only 1.15% of bovine kidney samples, Hg levels exceeded 0.3 mg/kg, while no such case was found in pigs. The results have conrmed the need to control Cd, Hg and Pb levels in bovine kidney tissue on slaughter line. At the same time, porcine kidney tissue is suitable for consumption by general population as Cd and Pb levels were below maximum permitted ones

POVIŠENE RAZINE OPASNIH ELEMENATA U TRAGOVIMA (CD, CU, PB, SE, ZN) U TKIVIMA PTICA U KONTEKSTU RAŠKIM UGLJENOM ONEČIŠĆENA OKOLIŠA

The mining and burning of Croatian Raša coal had resulted in release of various contaminants into the local environment. They have remained in the local soil, water, and plants, and became available to animals through their consumption. In this study, tissue samples from a total of 12 birds from the Raša area and 8 birds from a control area were subjected to multi-element analysis (Al, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Mo, Cd, Pb) by ICP-MS. The obtained results showed increased Se and Cd concentrations in some bird tissue samples compared to the control area. The highest concentrations of Cu, Zn, and Se were found in the liver, while the highest concentrations of Cd and Pb were found in the kidneys. Although some hazardous trace elements were elevated in the tissues of game species, the risk of consuming meat and offal of such species has been found to be very low.Rudarske i industrijske aktivnosti povezane s raškim ugljenom rezultirale su ispuštanjem raznih onečišćujućih tvari u lokalni okoliš. Te tvari i dalje su prisutne u lokalnome tlu, vodi i biljkama te su dostupne životinjama unosom hrane. U ovome istraživanju uzorci tkiva ukupno 12 ptica iz područja Raše te 8 ptica iz kontrolnoga područja podvrgnuti su multielementnoj (Al, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Mo, Cd, Pb) analizi s pomoću metode ICP-MS. Dobiveni rezultati pokazali su povišene koncentracije Se i Cd u nekim uzorcima tkiva ptica u usporedbi s kontrolnim područjem. Najveće koncentracije Cu, Zn i Se nađene su u uzorcima jetre, dok su najviše koncentracije Cd i Pb nađene u bubrezima. Iako su neki opasni elementi u tragovima povišeni u tkivima prikupljenih divljih ptica, analizom podataka utvrđeno je da je rizik od prehrambena unosa (meso i iznutrice) tih vrsta vrlo nizak

Dioxins in food chain

Sažetak Dioksini i dioksinima slični spojevi objedinjuju 29 različitih kongenera dioksina, furana i polikloriranih bifenila (PCB). Toksičnost navedenih spojeva vrlo je slična. Najtoksičniji kongener je 2,3,7,8-tetrakloro-dibenzo-p-dioksin (TCDD). Toksični potencijal ostalih dioksina (PCDD) i furana (PCDF) definira se u odnosu na TCDD. Izloženost ljudi dioksinima uglavnom se odnosi na izloženost preko hrane. Kada dioksini dospiju u organizam, dijelom se metaboliziraju i eliminiraju iz organizma, a dijelom se akumuliraju u masnom tkivu. Zakonskim propisima regulirano je da se udio dioksina u hrani i hrani za životinje izražava toksičnim ekvivalentom (TEQ).Dioxins and dioxin-like compounds include 29 different congeners of dioxins, furans and polychlorinated biphenyls (PCB). Toxicity of the listed compounds is very similar. The most toxic congener is 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Toxic potential of other dioxins (PCDD) and furans (PCDF) is defined in relation to TCDD. Human exposure to dioxins mainly refers to exposure through food. When dioxins enter the organism, they are partly metabolized and eliminated from the organism, and partly accumulated in the fatty tissue. It has been legally regulated that the share of dioxins in food and animal food is expressed by the toxic equivalent (TEQ)

Arsenic and arsenic speciation in foods, with an accent on inorganic arsenic

Specijacija metala je važna prilikom istraživanja toksičnosti i bioraspoloživosti elemenata kada je informacija o ukupnoj koncentraciji elementa nedovoljna. Najviše koncentracije ukupnog arsena izmjerene su u sljedećim prehrambenim proizvodima: riba i plodovi mora, proizvodi ili dodatci prehrani na bazi alga (osobito hijiki, Hizikia fusiformis), žitarice i proizvodi od žitarica, proizvodi od riže, mekinje i klice. Nisu svi arsenovi spojevi pronađeni u hrani jednako toksični i stoga mjerenje ukupnog sadržaja arsena u hrani ne znači nužno i mogući zdravstveni rizik. Plodovi mora (riba i školjke) sadrže visoke koncentracije ukupnog arsena (do 6 mg/kg mokre mase), no mogu sadržavati gotovo nedetektibilne koncentracije (manje od 0,001 mg/kg mokre mase) anorganskog arsena. U takvima slučajevima je sav arsen prisutan u oblicima arsenobetaina i arsenokolina koji se smatraju netoksičnim. Glavne tehnike koje se koriste za određivanje arsena u biološkim uzorcima su grafitna tehnike atomske apsorpcijske spektrometrije (GF-AAS), induktivno spregnuta optička emisijska spektrometrija (ICP-OES), spektrometrija masa s induktivno spregnutom plazmom (ICP-MS) i atomska apsorpcijska spektrometrija-hidridna tehnika (HG-AAS). Kombinirana tehnika tekućinske kromatografije visoke djelotvornosti i spektrometrije masa s induktivno spregnutom plazmom (HPLC-ICP-MS) je najmoćnija metoda za određivanje specijacije arsena u granicama detekcije od 0,5 μg/L. Zbog toksičnih učinaka anorganskog oblika arsena 1989. zajednička komisija Organizacije za hranu i poljoprivredu Ujedinjenih naroda i Svjetske zdravstvene organizacije (FAO/ WHO) je postavila privremeno dopuštenu količinu tjednog unosa (PTWI) za anorganski arsen od 15 μg/kg t.m/dan. U 2014. godini EFSA je evaluirala prehrambenu izloženost anorganskom arsenu u europskoj populaciji i podastrijela informacije o razinama arsena (ukupnog i anorganskog) u hrani europskog tržišta. Zaključeno je da je za sve uzraste, osim za dojenčadi i ostalu djecu, glavni doprinos izloženosti hrani pripada skupini prerađenih proizvoda na bazi žitarica (bez riže). Ostale skupine hrane koje su znatno pridonijele izloženosti iAs bili su: riža, mlijeko i mliječni proizvodi (glavni doprinos u dojenčadi i ostale djece) i pitka voda.Metal speciation is important in the study of element toxicity and bioavailability when information on the total concentration of the element is lacking. The highest total arsenic levels have been measured in the following foods: fish and seafood, products or supplements based on algae (especially hijiki, Hizikia fusiformis) and cereals and cereal products, with particularly high concentrations in rice grains, rice-based products, bran and germ. Not all arsenic compounds found in foods are equally toxic, and therefore measuring the total amount of arsenic in food does not necessarily imply a possible health risk. Seafood (fish and shellfish) containing high concentrations of total arsenic (up to 6 mg/kg of wet weight) may contain almost undetectable concentrations (less than 0.001 mg/kg of wet weight) of inorganic arsenic. In such cases, all arsenic compounds presented as arsenobetaine and arsenocholine forms are considered non- toxic. The main techniques used for the determination of arsenic in biological samples are graphite furnace atomic absorption spectroscopy (GF-AAS), inductively coupled optical emission spectrometry (ICP-OES), inductively coupled plasma optical emission spectrometry (ICP-MS) and hydride technique of atomic absorption spectrometry (HG-AAS). The combined technique of high performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC- ICP-MS) is the most powerful technique for the determination of arsenic speciation, and hasadetectionlimitof0.5μg/L.In1989,the toxic effects of inorganic arsenic forms led the Joint Commission of Food and Agriculture Organization of the United Nations and World Health Organization (FAO/WHO) to set a provisional tolerable weekly intake (PTWI) for inorganic arsenic of 15 μg/kg of body weight per day. In 2014, EFSA evaluated the dietary exposure to inorganic arsenic in the European population. It concluded that for all age groups except infants and toddlers, the main contributor to dietary exposure to inorganic arsenic is the food group of grain-based processed products (non-rice-based). Other food groups that were important contributors to inorganic arsenic exposure were rice, milk, and dairy products (the main contributor in infants and toddlers), and drinking water

Razlike u koncentracijama esencijalnih elemenata u mlijeku kobila hrvatskih hladnokrvnjaka i primorsko-dinarskih magarica

The concentrations of essential elements in the milk of Croatian Coldblood mares and Littoral- Dinaric donkey were measured. The mean element contents in horse milk were (mg/kg): Ca 687.1, Mg 72.1, K 637.7, Na 143.5, Cu 0.126, Fe 0.235, Se 0.01, Zn 2.06, Mn<0.01. In donkey milk, the mean element contents were (mg/kg): Ca 815.4, Mg 80.8, K 887.7, Na 217.6, Cu 0.027, Fe 0.196, Zn 2.36, Mn 0.016. In horse milk, moderate correlations were found between the elements: Ca-K, Mg-Se, Mg-K, Mg-Cu, Se-Cu, Se-Fe, Mn-K. Strong correlations were found among elements in donkey milk: Ca-Na, Ca-K, Ca-Cu, K-Na, K-Cu, Cu-Mn. Significant differences between Na, K and Cu concentrations were obtained between the two species. Other elements concentrations were similar in both species.Određene su koncentracije esencijalnih elemenata u mlijeku kobila hrvatskih hladnokrvnjaka i primorsko-dinarskih magarica. Srednje vrijednosti koncentracija elemenata u mlijeku kobila su (mg/ kg): Ca 687,1; Mg 72,1; K 637,7; Na 143,5; Cu 0,126; Fe 0,235; Se 0,01; Zn 2,06; Mn<0,01. U mlijeku magarica određene su srednje koncentracije elemenata (mg/kg): Ca 815,4; Mg 80,8; K 887,7; Na 217,6; Cu 0,027; Fe 0,196; Zn 2,36; Mn 0,016. U mlijeku kobila utvrđena je srednja korelacija između elemenata: Ca-K, Mg-Se, Mg-K, Mg-Cu, Se-Cu, Se-Fe, Mn-K. U mlijeku magarica utvrđena je jaka korelacija između elemenata: Ca-Na, Ca-K, Ca-Cu, K-Na, K-Cu, Cu-Mn. Statistički značajne razlike u koncentracijama Na, K i Cu utvrđene su u mlijeku tih dviju vrsta. Koncentracije drugih elemenata su slične u obje vrste