Occurrence, bioconcentration, and human health risks of pharmaceuticals in biota in the Sea of Marmara, Türkiye.

The presence, bioconcentration, and health risk via seafood consumption of 11 pharmaceutical compounds belonging to different therapeutic groups (anti-inflammatory, antiepileptic, lipid regulators, and hormones) were investigated in the muscle tissues of fish and the meat of shrimp in the Sea of Marmara. Six biota species (Merlangius merlangus, Trachurus meditterraneus, Serranus hepatus, Pomatomus saltatrix, Parapenaeus longirostris, Spratus sprattus) were collected from the five stations in October and April 2019. Ultrasonic extraction method followed by solid phase extraction was used for extraction of pharmaceutical compounds from biota samples and then analyzed using high-performance liquid chromatography. Of the 11 compounds, 10 were detected in biota species. Ibuprofen was the most frequently detected pharmaceutical in the biota tissues at high concentrations (<3.0-1225 ng/g, dw). The other widely detected compounds were fenoprofen (<3.6-323 ng/g, dw), gemfibrozil (<3.2-480 ng/g, dw), 17α-ethynylestradiol (<2.0-462 ng/g, dw), and carbamazepine (<7.6-222 ng/g, dw). The bioconcentration factors of the selected pharmaceuticals calculated in various aquatic organisms ranged from 9 to 2324 L/kg. The estimated daily intakes of anti-inflammatories, antiepileptics, lipid regulators, and hormones via seafood consumption were 0.37-568, 1.1-324, 8.5-197, 3-340 ng/kg bw. Day, respectively. Based on hazard quotients, estrone, 17ß-estradiol, and 17α-ethynylestradiol may pose a health risk to humans through the consumption of this seafood.

Melatonin pretreatment modulates anti-inflammatory, antioxidant, YKL-40, and matrix metalloproteinases in endotoxemic rat lung tissue.

We aimed to investigate the effects of melatonin administered before and during endotoxemia on the lung tissue of rats, cytokine, YKL-40, matrix metalloproteinase (MMP) and inhibitor levels, oxidative stress parameters, and energy balance. Sepsis was induced with lipopolysaccharide (LPS), the cell wall molecule of gram negative bacteria. Rats were divided into four groups, Control, LPS (Escherichia coli O127:B8, 20 mg/kg), melatonin (10 mg/kg), and melatonin+LPS (M+LPS). After injections, lung tissues samples were taken for experimental analyses. YKL-40, thiobarbituric acid reactive substances (TBARS), glutathione reductase (GR), glutathione peroxidase (GSH-Px), superoxide dismutase (SOD) enzymes levels were measured, high-energy components were analyzed; tumor necrosis factor-alpha (TNF-α), MMP-2, YKL-40, MMP-9, myeloperoxidase (MPO), tissue inhibitors of matrix metalloproteinase (TIMP)-1, and interleukin (IL)-10 immunoreactivities were investigated. In LPS group, YKL-40, creatine phosphate (both, p < 0.05), SOD, GR, adenosine mono-phophate (AMP), adenosine tri-phosphate (ATP) (for all, p < 0.01) were significantly decreased, while TBARS and adenosine di-phosphate (ADP) levels were increased (p < 0.01, p < 0.05; respectively) compared to other groups. MMP-2 and -9, TIMP-1, TNF-α, IL-10, and MPO immunoreactivity were investigated in LPS group. On the contrary, in M+LPS group, MMP-9, TIMP-1 immunoreactivities were not found and IL-10 and MMP-2 immunoreactivities were found with little involvement. In M+LPS group, YKL-40, GR, AMP, ATP, creatine phosphate (for all, p < 0.05), and SOD (p < 0.01) levels were significantly increased and TBARS levels were decreased (p < 0.05). In our study, we suggest that melatonin exerts a protective and curative effect by reducing the matrix metalloproteinase levels responsible for tissue damage balance, stimulating the release of antioxidant enzymes, regulating cytokines and energy balance during endotoxemia.

Occurrence, sources and environmental risk assessment of pharmaceuticals in the Sea of Marmara, Turkey.

In the present study, the occurrence and spatial distribution of selected eleven pharmaceuticals were investigated in the Sea of Marmara, Turkey. Samples were collected from different depths of the nine stations in April and October 2019. Pharmaceuticals were analyzed using liquid-liquid and solid-phase extraction (SPE) methods followed by high-performance liquid chromatography (HPLC). All target pharmaceutical compounds were detected at least once in the study area. Gemfibrozil, which belongs to the lipid regulatory group, was the most frequently detected in seawater at high concentrations (<0.016-9.71 µg/L). Ibuprofen (<0.015-2.13 µg/L) and 17α-ethynylestradiol (<0.010-3.55 µg/L) were identified as the other frequently detected pharmaceuticals. In addition, the presence of these selected compounds in April was higher than in October. According to the risk assessment results, naproxen, diclofenac, clofibric acid, gemfibrozil, 17ß-estradiol, and 17α-ethynylestradiol represent a high risk to aquatic organisms in the Sea of Marmara. These findings underline the importance of continued monitoring of these compounds as relevant organic contaminants in the study area to take appropriate measures to protect the ecosystem and, ultimately, human health.

Assessment of distribution of heavy metals and activity level of 210Pb in biota from the northern coast of the Marmara Sea and Western Black Sea.

In this study, heavy metals (Cd, Co, Cu, Ni, Pb, Zn, V) and 210Pb analyses have been performed in the marine biota (scaldfish, sea lettuce, crab). Samples were collected from 5 different parts of the Marmara Sea and Western Black Sea in January 2020. The results indicated that the highest Cu and Zn content was found in algae samples, but it was observed that heavy metal concentrations such as Co, Cu, Cd and V were generally low and under permissible limit. Also, 210Pb (radioactive isotope of Pb) activity levels were determined to vary from 23.20 Bq kg-1 to 52.67 Bq kg-1 dry weight. It was clearly seen that there was a linear correlation between the toxic and radioactive Pb when the obtained data were compared.

Monitoring the antioxidant activities by extracting the polyphenolic contents of algae collected from the Bosphorus.

The identification and quantification of ascorbic acid, phenolic acids and flavonoids were carried out simultaneously with a rapid method of reverse-phase high-performance liquid chromatography (RP-HPLC). Total flavonoid contents were being determined by UV-Vis spectrophotometry, and total phenolic contents were determined by UV-Vis spectrophotometry using the Folin-Ciocalteu Reagent (FCR) method. In all of the individual contents and total phenolic content analysis, the best results were obtained with the methanol-water solvent system. The methanol-hexane solvent system was selected as the best for the extraction of total flavonoid contents. The reason for this difference is the flavonoids in the analyzed samples which were the lipophilic character. Examining the algae species, the highest contents were achieved from Ulva lactuca and Ceramium rubrum species. Depending on industrial activity and the population density, regional characteristics have been shown to be effective in the changes of these contents which show antioxidant properties.

Comparison and origins of polycyclic aromatic hydrocarbons (PAHs) in the entrance and the exit of the Turkish Straits System (TSS).

Investigations of total petroleum hydrocarbons (TPHs) in water and polycyclic aromatic hydrocarbons (PAHs) in sediments were performed in the entrance and the exit of the Turkish Straits System (TSS) in autumn of 2016 and spring of 2017. TPH and PAH values ranged from 1.7 to 11.6 µg/l and 120 to 2912 ng/g (dw), respectively. On the basis of the given surface fluxes of the TSS, average petroleum flows were calculated as 1631 t/y from the Black Sea to the Marmara Sea and 8484 t/y from the Marmara Sea to the Aegean Sea. Pollution by PAHs ranged from relatively moderate to high. The most polluted sediments were collected from regions affected by shipping, such as Riva and Seddülbahir located at the entrance and the exit of the TSS, respectively. Moreover, origins of PAHs were determined using the ratios of PAH congeners. The main origins of PAHs were found as both pyrolytic and petrogenic at most stations.

Sources of metal pollution in the urban atmosphere (A case study: Tuzla, Istabul).

In this study, Istanbul-Tuzla Region atmosphere was selected as the working area for atmospheric pollution. Although the study area seems too local, this region contains shipyards and shipyard-related side product industries. It is also surrounded by aluminum (ASSAN) and copper (SARKUYSAN) facilities and tannery organized industrial district. For determined the atmospheric inputs, the sample collection was carried out as monthly in 2010. Particulate matter was filtered from aerosols via a high volume air sampler. The collected 46 ambient air samples were analyzed for Cr, Fe, Cu, Zn, Cd, Pb and Al using Atomic Absorption Spectrometry (AAS), Flame unit. Additionally, the volume of the air was drawn and meteorological data recorded. Average individual heavy metal concentrations were found as Cd (0.06 ng/m(3)) < Cr (0.09 ng/m(3)) < Zn (0.21 ng/m(3)) < Pb (0.23 ng/m(3)) < Cu (0.48 ng/m(3)). The concentrations of crustal elements Fe and Al were changed between 5.48 ng/m(3), 74 ng/m(3) and 14 ng/m(3), 284 ng/m(3) respectively during the sampling period. Except Cr and Fe anthropogenic contribution was seen on the concentrations of Zn, Cu, Pb and Cd in an increasing order. While the crustal element Fe was not show an appreciable change in concentration, but the Al concentration was display an important change in concentration depending on the wind transportation.

T-PAH contamination in Mediterranean mussels (Mytilus galloprovincialis, Lamarck, 1819) at various stations of the Turkish Straits System.

Mussels (Mytilus galloprovincialis) from the Turkish Straits Systems were analyzed for sixteen parent polycyclic aromatic hydrocarbon (PAH) contents by high performance liquid chromatography (HPLC). This marine organism was selected because of its multitude, wide distribution, being bio indicator for the pollution and consumption by humans. Total PAH concentrations ranged from 1.2 to 589 µg g(-1) in Istanbul Strait, 0.94-36.4 µg g(-1) in Marmara Sea and 0.4-47.9 µg g(-1) in Çanakkale Strait during the samplings. According to the results Istanbul and Çanakkale Straits are more polluted than the Marmara Sea.

Polybenzoxazine: a powerful tool for removal of mercury salts from water.

A reusable macroporous polybenzoxazine resin with high specific surface area was prepared as sorbent material for the removal of mercury salts. For this purpose, allyl-functionalized bis-benzoxazine was cured in dimethyl sulfoxide by thermally activated ring-opening polymerization at 180 °C for 3 d followed by a freeze-drying process. The porous structure of the resin was confirmed by SEM analysis and N2 adsorption/desorption studies at 77.3 K. Among various metal ions, namely, Pb(II), Fe(II), Mn(II), Cu(II), Zn(II), and Cd(II), the porous polybenzoxazine resin exhibited a specific sorption behaviour towards Hg(II). Mainly chemisorption and to some extent adsorption mechanisms were proposed for the observed high loading capacity of the resin. As evidenced by FTIR spectral analysis, the chemisorption is attributed to the coordination system formed between free OH and tertiary amino groups in the polybenzoxazine structure and Hg(II) ions. It was also demonstrated that the porous polybenzoxazine can be regenerated simply by treatment with acids. The resin was recycled for up to seven cycles without any significant loss of activity, as proved by sorption and desorption experiments.

Association of Pb, Cd, and Se concentrations and oxidative damage-related markers in different grades of prostate carcinoma.

Prostate cancer is known to be affected by the heavy metal levels and oxidative damage of the body, yet there are very few studies which look into the way it occurs. The aim of this study was to determine whether blood and tissue lead (Pb), cadmium (Cd), and selenium (Se) levels are associated with oxidative damage in the context of prostate cancer progression and development. Seventy-nine patients comprising 25 patients with benign prostatic hypertrophy (BPH), 23 patients with malignant prostatic carcinoma (malign Ca), 16 patients with low-grade prostatic intraepithelial neoplasia (LGPIN), and 15 patients with high-grade prostatic intraepithelial neoplasia (HGPIN) diagnosed on the basis of their clinical profile, transrectal ultrasonography, and histopathology were included in this study. Cd and Pb levels in whole blood were found to be increased in patients with HGPIN compared with the BPH group; also, the levels of Cd in whole blood and tissue were found to be increasing in patients with malign Ca, unlike BPH patients. Moreover, the levels of malondialdehyde (MDA) in plasma and tissue were significantly increased in malign Ca, LGPIN, and HGPIN than those in BPH. However, the levels of tissue Pb were found to be decreasing in BPH, unlike the malign Ca and HGPIN patients, and the levels of tissue protein carbonyls in malign Ca were significantly lower than those in HGPIN. The levels of tissue reduced glutathione (GSH) in malign Ca were significantly lower than those in BPH. Additionally, the levels of Se in serum and tissue in LGPIN were significantly lower than those in BPH. The serum Se levels in HGPIN were also significantly lower than those in BPH and malign Ca groups. Furthermore, the concentrations of serum Se in LGPIN were significantly lower than those in malign Ca. From the Pearson correlation analysis, there were significant positive correlations between tissue Cd and MDA levels in malign Ca, LGPIN, and HGPIN and between the tissue Pb and tissue MDA and protein carbonyl levels in malign Ca. Blood Pb and tissue Pb were also significantly positively correlated with plasma MDA and protein carbonyl levels in malign Ca. In addition, blood Pb was significantly positively correlated with tissue MDA and protein carbonyl levels in malign Ca, and a significant positive correlation was also found between blood Cd and plasma protein carbonyls and tissue MDA in LGPIN. We observed that altered prooxidant-antioxidant balance and heavy metal levels may lead to an increase in oxidative damage and may consequently play an important role in prostate carcinogenesis. These findings indicate that changes in the levels of Pb, Cd, Se, MDA, protein carbonyls, and GSH in the blood and/or tissue are related to the prostatic carcinoma development and progression, although triggering one of the mentioned changes is unknown; therefore, further study is required to determine the exact steps of the process and clarify the roles of different substances in order to obtain a more detailed explanation of the phenomenon.

Petroleum hydrocarbon contamination of the Southern Black Sea Shelf, Turkey.

INTRODUCTION: In this study, total petroleum hydrocarbon (TPH) contents and some aliphatic and aromatic hydrocarbon concentrations were analysed in coastal sediments of hot points collected from along the Southern Black Sea Shelf. MATERIALS AND METHODS: Surface sediment (0-2 cm) samples were collected from the locations using a Van Veen type grab sampler in September 2008 during a cruise on the Pollution Monitoring R/V ARAR. All sampling procedures were carried out according to internationally recognized guide-lines (UNEP 1991). Samples were analysed using a UV-fluorescence spec-trophotometry (UNEP/IOC/IAEA 1992) and gas chromatog- raphy (GC) via a Hewlett-Packard HP6890N series with a selective detector (GC-MSD) after hexane/ dichloromethane extraction. RESULTS AND DISCUSSION: The ratio C(17)/C(18) varied between 2.2 and 2.9 for the surface sediments of TRK 34Y (Samsun), TRK46 (Giresun), and TRK55 (Rize), respectively. These results showed higher marine organic matter accumulation. However, pyrolytic PAHs were found predominant in these areas. In contrast, petrogenic contributions were found at Stations TRK1 (Igneada), TRK13 (Zonguldak), TRK53 (Trabzon) and TRK61 (Hopa). TPH contents of surface sediments varied between 0.29 and 363 µg g(-1) (dry wt) throughout the shelf. The lowest values were measured at Stations TRK1 (Igneada) and TRK 19 (Bartin), whereas the highest values were found at Stations TRK13 (Zonguldak) and TRK 53 (Trabzon).

Toxic metal (Pb, Cd, As and Hg) and organochlorine residue levels in hake (Merluccius merluccius) from the Marmara Sea, Turkey.

Toxic metals (Pb, Cd, As and Hg) and organochlorine residue levels were measured in hake (Merluccius merluccius) from the Marmara Sea. Biota samples were collected by a trawling cruise of the R/V ARAR in August and December 2009. The concentrations of toxic metals varied between Pb, 3.23-14.4; Cd, <0.01-2.14; Hg, 0.01-0.18 and As, 0.01-0.21 [Formula: see text]g g(-1) dry wt. Pb levels in the Marmara Sea were found to be higher than the critical limits set by the both Turkish Ministry of Environment for Aquatic Products (1 µg g(-1) wet wt.) and European countries (2.0 µg g(-1), UNEP 1985). In contrast, As and Hg levels were found to be lower than the critical limits for two periods. Cd contents of fish from the Marmara Sea were also comparable to or slightly lower than contents of fish from the Southern Black Sea Shelf. The results of organochlorine residues ranged between total HCH, <0.05 and 99 ng g(-1); endrin, <0.001 and 381 ng g(-1); alpha-endosulphan, <0.05 and 90 ng g(-1); beta-endosulphan, <0.05 and 15.3 ng g(-1); o,p DDE, 3.5 and 52.4 ng g(-1); p,p DDE, 7.4 and 139 ng g(-1); o,p DDD, 1.5 and 90.2 ng g(-1) and p,p DDD, 2.7 and 86 ng g(-1) wet weight. The rivers for the distribution of organochlorine levels in the Marmara Sea ordered from highest to lowest as Dil R. > Susurluk R. > Biga R. > Gönen R. The high levels of o,p and p,p DDE, and o,p and p,p DDD compounds, which are metabolites of DDT, indicate its illegal use. Toxic metal and organochlorine residue levels of fish are significantly higher than levels from the Mediterranean Sea.

Biogeochemical cycle of arsenic and calculating the enrichment factor by using Li element.

In this study, the biogeochemical cycle of arsenic in the Bosporus and the Golden Horn, which have a two-layer stratified structure, was investigated and the dominant feature in this cycle was observed to be the anthropogenic (domestic + industrial) activities. On the contrary, in the rural areas which are far from human activities, such as Igneada, the seawater-atmosphere interchange can be observed evidently in the periods covering the primary production.

Total metal levels in crayfish Astacus leptodactylus (Eschscholtz, 1823), and surface sediments in Lake Terkos, Turkey.

The aim of this study was to determine the total metal accumulation (aluminium, copper, manganese, lead, cadmium and iron) in different organs and eggs of Astacus leptodactylus (Eschscholtz, 1823) and sediments total metal contents (aluminium, copper, manganese, lead, cadmium, iron, zinc, chromium, nickel) in Lake Terkos. Water and sediment samples were collected from two stations at two different depths (1 and 2 m) of Lake Terkos in May 2008. Crayfish samples were collected by trammel net at the same region. Primary hydrographic conditions, such as temperature (13.6-19.4 degrees C), salinity (0.27-0.34 per thousand), dissolved oxygen (7.04-12.30 mg l(-1)) and pH (7.42-8.51), were recorded for each sampling point. Moreover, the total organic carbon (1.65-5.44%) and the total calcium carbonate contents (19.44-41.16%) of sediment samples were determined. According to the Turkish Food Codex (J Zool 26:283-288, 2002), the maximum allowable Pb and Cd levels in crayfish are 0.5 mg/kg wet weight. Accordingly, the Pb and Cd levels determined in A. leptodactylus samples are below this limit. However, when compared with the acceptable metal limits defined by WHO, Australian National Health and Medical Research Council and Ministry of Agriculture in United Kingdom (UK), it is clear that the Cu level is at the limit and the Cd results exceed the limit. When the metal contents in sediment samples from Lake Terkos are examined, it is seen that the Al, Fe, Mn, Ni and Cu contents are lower while Zn, Cr, Cd and Pb contents are higher than the crustal average values. The high values draw attention to the land-based domestic and industrial inputs. Lake Terkos sediments have high enrichment factors (EF) of Zn, Cr, Cd and Pb metals which corroborate this result. The low EFs of Fe, Ni and Cu are due to the natural (terrigeneous) inputs. Additionally, there is no Al, Fe, Ni and Cu metal enrichment in these lake sediments because of the low contamination factor (CF) values. However, it is moderately contaminated by Zn, Cr and Pb, and heavily contaminated by Cd.

Heavy metal concentrations in water, suspended matter, and sediment from Gökova Bay, Turkey.

The contents of heavy metals (Fe, Mn, Pb, Cu, Cd, and Hg) dissolved in water and suspended solids of Gökova Bay--partly and fully sampled in 2005 and 2006, respectively--are quite higher than the average values encountered in uncontaminated sea water. The high concentrations are associated with terrestrial inputs from the mining zones and anthropogenic (domestic+industrial) sources. Moreover, the distribution of Fe and Cu is affected by primary production because these elements function as nutrients in biological activities. The Cr, Ni, and Fe concentrations of surface sediments are above the shale average. The Cr and Ni contents of surface sediments representative of river mouths strongly correlate with total phosphorus contents. In a sulfide-poor environment, Pb and Cu were concentrated at a higher ratio in surface sediments than Cd, probably due to higher stabilities of their surface complexes with amorphous iron oxides and clay minerals existing as major components in the sediments. The exceptional enrichment of Zn may be attributed to double oxide formation with amorphous iron oxides in sediments. The high metal values are most probably caused by terrestrial inputs from anthropogenic sources and the mining zones at the southeast part of the bay. The Al, Mn, Pb, Cu, Zn, and Hg contents are below the shale average. The low values have possibly originated from the coarse-grained sandy sediments having a low affinity for metals. There are no distinct differences in the metal distributions in water and suspended matter between the years 2005 and 2006 in the bay, probably due to low sedimentation rates.