J. Falandysz

Chloronaphthalenes as food-chain contaminants: a review

Chloronaphthalenes are dioxin-like environmental and food contaminants that for many years have undergone diffusion from dispersed emission sources of various types on a global scale. When released into ambient air like many other semivolatile organohalogen compounds, chloronaphthalenes undergo various processes and pathways including sequestering by plant vegetation and biota. Recently available data indicate that sequestering rates of chloronaphthalenes by plant biomass and including edible plants as well as concentrations in food sources of plant origin can be greater than was earlier predicted. Additionally, it become known very recently that in some highly industrialized countries such as Japan, Canada and the UK, the technical chloronaphthalene mixtures are still a subject of industrial and commercial interest, even if such activities are illegal. Recent achievements in HRGC-HRMS have enabled elucidation and quantification of the chloronaphthalene congener composition in environmental matrices, food sources and technical mixtures, their persistency, environmental fate, accumulation in biota and potential for food chain biomagnification. However, at the same time this raised questions regarding human exposure to these compounds. By the late 1990s, these developments added to the relatively rapidly growing knowledge on these compounds and especially individual congener properties such as thermodynamic and physicochemical features and toxicity. Multistage fractionation has recently enabled routine congener-specific quantification of tetra- to octachloronaphthalene in various matrices. This paper reviews the literature on chloronaphthalenes as food chain contaminants and covers their origin, physicochemical properties, toxicity, environmental concentrations and persistency, and homologue group and congener composition in various matrices. The review also covers distribution in environmental compartments and subsequent fate and migration to food sources, as well as the magnitude of dietary intake and human body concentrations. Data on chloronaphthalene residues in food, however, are still scare, an exception being seafood sources and recently available data from Spain on their concentrations in staple foods and dietary intake.

Multivariate characterization of elements accumulated in King Bolete Boletus edulis mushroom at lowland and high mountain regions.

Based on ICP-MS, ICP-OES, HG-AAS, CV-AAS and elementary instrumental analysis of King Bolete collected from four sites of different soil bedrock geochemistry considered could be as mushroom abundant in certain elements. Kings Bolete fruiting bodies are very rich in K (> 20 mg/g dry weight), rich in Ca, Mg, Na, Rb and Zn (> 100 μg/g dw), and relatively also rich in Ag, Cd, Cs, Cu, Fe, Mn and Se (> 10 μg/g dw). The caps of King Bolete when compared to stipes around two-to three-fold more abundant are in Ag, Cd, Cs, Cu, Hg, K, Mg, Mo, N, Rb, Se and Zn. King Bolete collected at the lowland and mountain sites showed Ag, Ba, Co, Cr, Hg, K, Mg, Mn, Mo and Na in caps in comparable concentrations, and specimens from the mountain areas accumulated more Cd and Sb. Elements such as Al, Pb and Rb occurred at relatively elevated concentration in King Bolete picked up at the metal ores-rich region of the Sudety Mountains. Because of high bioconcentration potential King Bolete at the background sites accumulate in fruiting bodies great concentrations of problematic elements such as Cd, Pb and Hg, i.e. up to nearly 20, 3 and 5 μg/g dw, on the average, respectively. The interdependence among determined mineral elements examined were using the principal components analysis (PCA) method. The PCA explained 56% of the total variance. The metals tend to cluster together (Ba, Cd, Cs, Cr, Ga, Rb, Se, Sr and V; K and Mg; Cu and Mo). The results provided useful environmental and nutritional background level information on 26 minerals as the composition of King Bolete from the sites of different bedrock soil geochemistry.

Selected elements in fly agaric Amanita muscaria

Concentrations of Ag, Al, Ba, Ca, Cd, Co, Cu, Cr, Cs, Fe, Ga, Hg, K, Mg, Mn, Mo, Na, Pb, Rb, Se, Sb, Sr, V, Tl and Zn have been determined in the whole fruiting bodies, as well as separately in caps and stalks, of fly agaric collected from three geographically distant sites in northern part of Poland. The elements were determined using ICP-MS, ICP-OES, HG-AAS and CV-AAS, respectively. For elements such as Al, Ba, Cr, Fe, Ga, Mo, Mn, Pb, Sb, Sr, Tl, and V concentrations were similar in the caps and stalks, respectively, and for K, Zn, Ag, Ca, Cd, Cu, Hg, Mg, Rb and Se were greater in the caps, while for Co, Cs and Na in the stalks. For Ag, Al, Ba, Ca, Cd, Co, Cr, Cs, Fe, Ga, Hg, Mn, Mo, Pb, Rb, Sb, Sr, Tl and V concentration in the caps showed spatial variations (P < 0.05), while for Cu, K, Mg, Na, Se and Zn was independent of the site. The elements such as K with median or mean in the caps between 37,000 and 43,000 μg/g·dm and Mg with 920 and 1,100 μg/g dm were most abundant. Next, within median values range from approximately 100 to 500 μg/g dm were such as Ca, Fe and Al, and in descending order they followed by Rb (100–400 μg/g dm); V, Na, Zn (50–200 μg/g dm); Cu, Mn (10–50 μg/g dm); Cd (10–20 μg/g dm); Se (5 μg/g dm); Ba (< 1–3); Cr, Ag, Pb, Sr (< 1–2 μg/g dm); Cs, Co, Hg (< 1–1 μg/g dm); Ga (< 0.5), Sb, Mo and Tl (< 0.1 μg/g dm).

Content and bioconcentration of mercury in mushrooms from northern Poland.

Mercury (Hg) was quantified using cold vapour-atomic absorption spectrometry (CV-AAS) in the fruiting bodies of nine edible and five inedible mushrooms and in underlying soil substrate samples. In total, 404 samples comprising caps and stalks and 202 samples of soil substrate (0–10 cm layer) were collected in 1996 from Trójmiejski Landscape Park, northern Poland. Mean Hg concentrations in the soil substrate for different species varied between 10 ± 3 and 780 ± 500 ng g -1 dry wt (range 2.3–1700). Among edible mushroom species, Horse Mushroom (Agaricus arvensis), Brown Birch Scaber Stalk (Leccinum scabrum), Parasol Mushroom (Macrolepiota procera), King Bolete (Boletus edulis) and Yellow-cracking Bolete (Xerocomus subtomentosus) contained elevated concentrations of Hg ranging from 1600 ± 930 to 6800 ± 4000 ng g-1 dry wt in the caps. Concentrations of Hg in the stalks were 2.6 ± 1.1 to 1.7 ±1.0 times lower than those in the caps. Some mushroom species investigated had high Hg levels when compared with specimens collected from the background reference sites elsewhere (located far away from the big cities) in northern Poland. Bioconcentration factors of Hg in the caps of Horse Mushroom, Parasol Mushroom and Brown Birch Scaber Stalk were between 150 ± 58 and 230 ± 150 ng g-1 dry wt, respectively, and for inedible Pestle-shaged Puffball (Claviata excipulformis) was 960 ± 300 ng g-1 dry wt. Linear regression coefficients between Hg in caps and in stalks and Hg soil concentrations showed a positive relationship for A. arvensis and Horse mushroom (p < 0.05) and a negative correlation for the caps of Death Caps (Amanita phalloides) and Woolly Milk Cap (Lactarius torminosus) (p < 0.05), while for other species no clear trend was found.

Mercury and its bioconcentration factors in Poison Pax (Paxillus involutus) from various sites in Poland

Data are presented on total mercury content of Poison Pax from 14 sites across Poland. Mercury was measured by cold-vapor atomic absorption spectroscopy (CV-AAS) after nitric (mushrooms) and nitric/sulphuric (soil substrate) acid digestion of the samples. Both the caps, stalks and whole fruiting bodies of Poison Pax exhibited mercury at relatively small concentration and for all sites the median values ranged from 0.01 to 0.10 μ g/g dm (the caps) and from 0.01 to 0.10 μ g/g dm (the stalks). The arithmetic means of mercury for most of the sites surveyed ranged from 0.01 ± 0.01 to 0.11 ± 0.06 μ g/g dm (the caps) and from 0.01 ± 0.01 to 0.11 ± 0.04 μg/g dm (the stalks). The cap to stalk mercury concentration quotient for 181 fruiting bodies of Poison Pax in this study was 1.4 ± 0.5 with range from 0.4 to 5.4, and for the particular sites were from 0.6 ± 0.2 to 2.5 ± 1.2. The total mercury content of top soil (0–15 cm) layer for most of the sites was within a range from 0.02 ± 0.01 to 0.05 ± 0.04 μ g/g dm, while from 0.06 ± 0.02 to 0.07 ± 0.04 μ g/g dm were for two sites in the Tucholskie Forest, and 0.10 ± 0.04 and 0.09 ± 0.04 μ g/g dm were for an area near the industrial town of Starachowice and for the Kłodzka Hollow in the Sudety Mountains, respectively. Both the caps, stalks or whole fruiting bodies of Poison Pax were characterized by a relatively small bioconcentration factor (BCF) value of mercury with a median value between 0.2 and 3.3, 0.2 and 2.2 and 0.3.

Mercury and its bioconcentration factors in fly agaric (Amanita muscaria) from spatially distant sites in Poland

Total mercury content has been determined in the fruiting bodies of fly agaric (Amanita muscaria) and topsoil layer (0–10 cm) collected from 14 spatially distant sites across Poland. Mercury was measured by cold-vapor atomic absorption spectroscopy (CV-AAS) after nitric acid (mushrooms) or nitric acid and sulfuric acid (soil) digestion of the samples. The caps, depending on the site, contained total mercury at mean concentrations from 0.24 ± 0.13 to 1.4 ± 0.6 μg/g dm (median 0.19–1.4 μg/g dm), and stalks from 0.18 ± 0.06 to 0.71 ± 0.26 μg/g dm (median 0.18–0.67 μ g/g dm). An overall-mean the total mercury content for 204 caps and stalks was, respectively, 0.73 ± 0.55 (0.05–3.3 μg/g dm) and 0.43 ± 0.33 (0.09–2.3 μg/g dm).

Concentrations of heavy metals in the tissues of red deer (Cervus elaphus) from the region of Warmia and Mazury, Poland

Cadmium, lead, copper and zinc were quantified using a validated ICP/MS method in the tissues and organs of 82 specimens of red deer of different sexes and ages, which had been hunted at the Great Lakes Land region in the north-eastern of Poland in 2000–01. Copper and zinc occurred in liver, kidney and muscle tissue of red deer at concentrations of 6.4–29, 3.3–7.2 and 1.9–6.4, and of 19–43, 17–41 and 19–64 mg kg−1, respectively, which are considered typical for the species, age and gender compared with values noted for some other wild and domestic ruminant species elsewhere. For cadmium and lead, the concentrations decreased in the order kidney > liver > muscle tissue, with overall means of 2.2, 0.19, and 0.10, 0.31, and 0.26, 0.22 mg kg−1 wet weight, respectively. The cadmium content of the kidney of a proportion of red deer sampled exceeded the legal tolerance limits set in Poland. The means (but not individual animal data) obtained for cadmium in kidney and liver correlated (0.99) with the age of red deer. Also, the lead content of the muscle meat of red deer for many carcasses exceeded the legal limit, which was probably due to contamination from the fine dust particle remains from the lead bullets used.

Selected elements of Poison Pax Paxillus involutus

Concentrations of Ag, Al, Ba, Ca, Cd, Co, Cu, Cr, Cs, Fe, Ga, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, Rb, Se, Sb, Sr, V, Tl and Zn have been determined in the whole fruiting bodies as well as separately in caps and stalks of Poison Pax collected from three geographically distant sites across Poland. The elements were determined using ICP-MS, ICP-OES, HG-AAS and CV-AAS, respectively. Based on arithmetic mean and median values for Poison Pax specimens from the Leźno site the elements such as Ag, Co, Cr, Cs, Mn, Mo, K, Pb, Rb, Sb, Se, V and Tl occur at similar concentration both in the caps and stalks, while for Cd, Cu, Hg, Mg and Zn around two-fold greater concentrations were noted in caps than stalks (cap/stalk concentration quotient > 1). Cs, Cd, Ni and Rb occurred at much greater concentration in specimens collected from the K≪odzka Hollow in the Sudety Mountains when compared to the lowland site (Mann–Whitney U-test), and slightly greater values were noted also for Cr, Mo and Rb, while for Ca, Co, Mg and Mn were smaller The results provide useful environmental and biological baseline level of information for metallic elements of Poison Pax.

HRGC/HRMS Analysis of Chloronaphthalenes in Several Batches of Halowax 1000, 1001, 1013, 1014 and 1099

Chloronaphthalene (CN) congeners and homologue groups have been quantified in up to three batches of several types of technical CN formulations of the Halowax series (Halowax 1031, 1000, 1001, 1013, 1014 and 1099), to elucidate possible batch-to-batch compositional variations. Using isotope dilution and HRGC/HRMS a relatively large variation in CN congeners and homologues composition among the batches of particular types of the Halowax formulations could be noted, and also when compared to the composition declared by the manufacturer. Depending on the type of the Halowax formulation and its batch in total up to 54 peaks from chloronaphthalenes (Agilent Ultra 2 liquid phase), which represented 70 of 75 CN congeners theoretically possible, could be found in these mixtures. These congeners represented all CN homologue groups from mono- to octaCN but some co-eluted. A co-eluting congeners were such as: 1,4-/1,6- (nos. 5/7), 1,5-/2,7- (nos. 6/12), 2,6–1,7- (nos. 11/8) of diCNs; 1,3,6-/1,3,5- (nos. 20/19), 1,3,7-/1,4,6- (nos. 23/24), 1,6,7-/2,3,6- (nos. 25/26) of triCNs; 1,2,5,7-/1,2,4,6-/1,2,4,7- (nos. 37/33/34), 1,3,6,8-/1,2,5,6- (nos. 45/36), 1,2,3,5-/1,3,5,8- (nos. 28/43), 1,2,3,4-/1,2,3,7- (nos. 27/30), 1,2,5,8-/1,2,6,8- (nos. 38/40) of tetraCNs; 1,2,3,5,7-/1,2,4,6,7- (nos. 52/60), 1,2,3,5,8-/1,2,3,6,8- (nos. 53/55) of pentaCNs; 1,2,3,4,6,7-/1,2,3,5,6,7- (nos. 66/67), 1,2,3,4,5,7-/1,2,3,5,6,8- (64/68) and 1,2,4,5,6,8-/1,2,4,5,7,8- (nos. 71/72) of hexaCNs. Absent in the Halowaxes were CN congeners such as 1,3,8-triCN (no. 22) (<0.0002 mg/g), 1,3,6,7-tetraCN (no. 44), 1,2,3,6-TetraCN (no. 29), 1,2,3,6,7-pentaCN (no. 54) and 1,2,3,6,7,8-hexaCN (no. 70) (<0.0005 mg/g).

By-side impurities in chloronaphthalene mixtures of the Halowax series: all 209 chlorobiphenyls.

Abstract All seven Halowax formulations examined were contaminated with chlorophenols (CPhs). The total CPhs content of the CN mixtures ranged from 1050 to 34,200 ng/g. The absolute concentration of CPhs decreased with an increase of degree of chlorination (% Cl) of the Halowax 1031 (27%), 1000 (35%), 1001 (49%), and 1099 (51%), respectively, but remained relatively constant for higher chlorinated Halowax 1099 (51%), 1013 (54%), 1014 (59%), and 1051 (70%). 2,4,6-TrCPh and 2,4-DiCPh did contaminated all seven Halowax formulations and PeCPh remained undetected (<90 ng/g) only in Halowax 1099, while less frequently occurred 2,6-DiCPh and followed by 3-/4-MoCPh, 2,5-DiCPh, 2-MoCPh, 2,3-DiCPh, and 2,3,4,6-TeCPh. The CPh congeners such as 3,4-DiCPh, 3,5-DiCPh, 2,3,4-TrCPh, 2,3,5-TrCPh, 2,3,6-TrCPh, 2,4,5-TrCPh, 3,4,5-TrCPh, 2,3,4,5-TeCPh, and 2,3,5,6-TeCPh were undetected in any of the Halowax formulation examined. The profile (%) of higher chlorinated CPh homologues like PeCPh in the Halowaxes followed somehow a degree of chlorination (Cl %) of the parent mixture, i.e., increased from 14, 22, 43, 55, 52 to 80%, respectively, but exception was free of PeCPh the Halowax 1099. And contrary, for a lower chlorinated DiCPhs and TrCPhs their relative proportions decreased but again an exception was Halowax 1099. The fingerprint profiles of 2,4,6-TrCPh, 2,4-DiCPh, and PeCPh, which were usually the most abundant congeners varied and were less consisted when compared to the CPh homologue group profiles, and also more depended on the type of technical Halowax mixture. Due to absence of 2,4,5-TrCPh but presence of 2,4-DiCPh, 2,6-DiCPh, 2,4,6-TrCPh, and PeCPh, which, respectively, are indicative congeners for CPhs obtained by alkaline hydrolysis of chlorobenzenes or phenol chlorination using gaseous chlorine, just co-occurrence of phenol impurity in technical naphthalene is suggested as a solely source of CPhs in the Halowax mixtures.