Assessment of human health risk from heavy metals levels in water and tissues of two trout species (Oncorhynchus mykiss and Salmo coruhensis) from the Fırtına and Güneysu Rivers in Turkey

Human health risks were evaluated from consumption of heavy metal contaminated fish from the F?rt?na and Güneysu Rivers in Rize. The study was aimed to assess heavy metal load in water and two fish species. The potential human health risk due to consumption of Oncorhynchus mykiss and Salmo coruhensis was assessed by estimating average daily intake (EDI), target hazard quotient (THQ) and hazard index (HI) of metals. Our results showed that the levels of heavy metals in both water and two fish species are lower than the acceptable limit recommended by Food and Agricultural Organization (FAO) and World Health Organization (WHO).     

Accumulation of nodularin in sediments, mussels, and fish from the Gulf of Gdańsk, southern Baltic Sea

In the Gulf of Gdańsk, as in other parts of the Baltic Sea, toxic blooms of Nodularia spumigena are an annual phenomenon. In the present work, the accumulation of nodularin (NOD), a cyanobacterial pentapeptide hepatotoxin, in sediments, blue mussels, and flounders from the Gulf of Gdańsk was studied by enzyme-linked immunosorbent assay (ELISA). In the surface layers of the sediments NOD concentration ranged from 2.3 ng/g dry weight (dw) several months after cyanobacterial bloom to 75 ng/g dw during the bloom. The highest toxin content in mussels was 139 ng/g dw. In two sampling stations situated in the coastal waters of the Gulf of Gdańsk the concentrations of NOD in sediments and mussels were significantly lower than those measured in the Gulf of Finland. In sediments and mussels collected in the Gulf of Gdańsk, the toxin was also detected in March when N. spumigena did not occur. In flounder, NOD accumulated in the liver (489 ng/g dw), guts (21 ng/g dw), and gonads (21 ng/g dw). Hybride quadrupole-time-of-flight liquid chromatography/mass spectrometry/mass spectrometry (TOF-LC/MS/MS) confirmed the presence of NOD in sediment, mussel, and fish samples. Additionally, other NOD analogues, ([DMAdda(3)]NOD and [dhb(5)]NOD), were detected in sediments and mussel tissue. No NOD conjugates with reduced glutathione or cysteine were found in fish and mussels.     

Determination of nucleosides and nucleobases in different species of Cordyceps by capillary electrophoresis–mass spectrometry

In present study, a capillary electrophoresis–mass spectrometry (CE–MS) method was developed for the simultaneous analysis of 12 nucleosides and nucleobases including cytosine, adenine, guanine, cytidine, cordycepin, adenosine, hypoxanthine, guanosine, inosine, 2′-deoxyuridine, uridine and thymidine in natural and cultured Cordyceps using 5-chlorocytosine arabinoside as an internal standard (IS). The CE separation conditions and MS parameters were optimized systematically for achieving good CE resolution and MS response of the investigated compounds. The optimum CE electrolyte was 100 mM formic acid containing 10% (v/v) methanol. The optimum MS parameters were as follows: 75% (v/v) methanol containing 0.3% formic acid with a flow rate of 3 μL/min was selected as the sheath liquid; the flow rate and temperature of drying gas were 6 L/min and 350 °C, respectively. The optimized CE–MS method was successfully applied for the simultaneous determination of 12 nucleosides and nucleobases in natural and cultured Cordyceps. On the basis of quantitative results, the total content of nucleosides is much higher in cultured Cordyceps (9138 ± 4823 μg/g for cultured C. sinensis; 3722 ± 1446 μg/g for C. militaris) than in natural ones (2167 ± 412 μg/g). However, the hypoxanthine (131 ± 47 μg/g) and inosine (335 ± 90 μg/g) are much higher in natural C. sinensis. Cordycepin, which is abundant in cultured C. militaris (2276.5 ± 842.6 μg/g), is only found in natural C. sinensis with very low content and cannot be detected in the cultured ones.     

Micropollutants impair the survival of Oreochromis niloticus and threat local species from Iguaçu River,Southern of Brazil

The wastewater contamination of urban rivers is a concern for biodiversity and a consequence from poor urban conservation policies. In the current study, the impact of urban and industrial activities was investigated in Iguaçu river (Southern Brazil) using juvenile Oreochromis niloticus, after trophic and chronic exposure (25, 50 and 100 %), over 81 days. After exposure liver, gills, gonads, brain, muscle, and blood were sampled for chemical, biochemical, histopathological, genotoxic and molecular analyses. Water levels of persistent organic pollutants such as polychlorinated biphenyls, organochlorine pesticides, polycyclic aromatics hydrocarbon (PAHs) and metals were investigated. The redox unbalance, histopathological and increase in vitellogenin expression in fish revealed both the bioavailability of micropollutants and their harmful effects. According to the results, the level of Iguaçu river pollution negatively impacts the health of O. niloticus revealing and highlighting the risk of this pollution exposure to biota and human populations.     

Determination of propofol UDP-glucuronosyltransferase (UGT) activities in hepatic microsomes from different species by UFLC–ESI-MS

Propofol O-glucuronidation has been used as probe reaction to phenotype UGT1A9 activity in human liver, thus a sensitive and specific method for determination of propofol O-glucuronide (PG) is urgently desirable. In the current study, a new LC–ESI-MS method for determination of PG in hepatic microsomes from human (HLM), monkey (CyLM), dog (DLM), minipig (PLM), rat (RLM) and mouse (MLM) was developed and validated using 4-methylumbelliferyl-β-d-glucuronide as an internal standard (IS). PG and IS was separated by a Shim-pack XR-ODS column (100 mm × 2.0 mm, 2.2 μm, Shimadzu) under gradient conditions with the mobile phase of acetonitrile and water containing 0.2% acetic acid (v/v). The mass spectrometric detection was performed under selected ion monitoring (SIM) for PG at m/z 353 and IS at m/z 351. The assay exhibited linearity over the range 0.05–30 μM for PG with the correlation coefficient of 0.9995. The intra- and inter-day precision was less than 7.2%, with accuracy in the range 93.8–107.5%. The developed method was successfully used for characterizing interspecies and human individual differences in the O-glucuronidation activity towards propofol, as well as investigating inhibitory effects of androsterone and phenylbutazone on propofol O-glucuronidation in HLM.     

Effects of historical lead–zinc mining on riffle-dwelling benthic fish and crayfish in the Big River of southeastern Missouri, USA

The Big River (BGR) drains much of the Old Lead Belt mining district (OLB) in southeastern Missouri, USA, which was historically among the largest producers of lead–zinc (Pb–Zn) ore in the world. We sampled benthic fish and crayfish in riffle habitats at eight sites in the BGR and conducted 56-day in situ exposures to the woodland crayfish (Orconectes hylas) and golden crayfish (Orconectes luteus) in cages at four sites affected to differing degrees by mining. Densities of fish and crayfish, physical habitat and water quality, and the survival and growth of caged crayfish were examined at sites with no known upstream mining activities (i.e., reference sites) and at sites downstream of mining areas (i.e., mining and downstream sites). Lead, zinc, and cadmium were analyzed in surface and pore water, sediment, detritus, fish, crayfish, and other benthic macro-invertebrates. Metals concentrations in all materials analyzed were greater at mining and downstream sites than at reference sites. Ten species of fish and four species of crayfish were collected. Fish and crayfish densities were significantly greater at reference than mining or downstream sites, and densities were greater at downstream than mining sites. Survival of caged crayfish was significantly lower at mining sites than reference sites; downstream sites were not tested. Chronic toxic-unit scores and sediment probable effects quotients indicated significant risk of toxicity to fish and crayfish, and metals concentrations in crayfish were sufficiently high to represent a risk to wildlife at mining and downstream sites. Collectively, the results provided direct evidence that metals associated with historical mining activities in the OLB continue to affect aquatic life in the BGR.     

Ecotoxicological characteristics and ecological risk assessment of trace elements in the bottom sediments of the Rożnów reservoir (Poland)

Ecotoxicology - The bottom sediments in catchment areas behind dams play a significant role in water ecosystems. On the other hand, the structure of sediments makes them a natural geosorbent, in...     

Contamination and Biomarkers in the Great Blue Heron, an Indicator of the State of the St. Lawrence River

In 1996–1997, nine breeding colonies of the great blue heron on the St. Lawrence River and its estuary (Québec, Canada) were investigated in the framework of a biomonitoring program. Fledglings from colonies in freshwater were more contaminated with mercury, PCBs and many organic contaminants than those from estuarine colonies. The level of contamination in the St. Lawrence River is generally below the levels of toxicological effects for the great blue heron. The molar ratio of retinol: retinyl palmitate in heron eggs was correlated with total PCBs (r=0.79) and Mirex (r=0.90). In plasma, all biochemical parameters were significantly different between freshwater and marine colonies. Plasma retinol concentrations at the Dickerson and Hérons colonies were significantly lower compared with those at Grande Ile (p<0.05) and Steamboat (p<0.001). Based on retinoid and β-carotene concentrations in eggs, low plasma retinol was not associated with possible dietary deficiency. Plasma retinol was negatively correlated with many PCB congeners, total PCBs (r=−0.78), p,p′-DDE, trans-nonachlor and α-HCH. Similarly, the hormone T3 was correlated with many PCB congeners, total PCBs (r=−0.69) and the same organochlorine chemicals. Plasma LDH concentrations were different among freshwater colonies, Grande Ile and Hérons colonies having LDH values significantly greater than those of Steamboat (respectively, p<0.05 and p<0.01). Globally, the health status of the St. Lawrence great blue heron population was judged to be acceptable, however, several biomarkers indicated positive responses to contaminants.     

Determination of lead in samples of zooplankton,water, and sediments in a Mexican reservoir: Evidence for lead biomagnification in lower/intermediate trophic levels?

We have determined lead concentration of water, sediment, and zooplankton samples of El Niágara, a reservoir in Aguascalientes, Mexico. Our results include the first report of bioconcentration factor (BCF) obtained in an actual ecosystem (as opposed to the experimental setups in the laboratory) for a rotifer species; Asplanchna brigthwellii (BCF ca. 49 300). The BCF of this predatory zooplanktonic species (A. brigthwellii) are up to four times greater than those of two grazing zooplanktonic species (Daphnia similis and Moina micrura). In this contaminated reservoir that lacks fishes, Asplanchna, and Culex sp. together with ducks and other bigger invertebrates might represent the top predators. Our data suggest that biomagnification of lead through at least one trophic level can occur in freshwater systems. Biomagnification in A. brigthwellii might be explained in part by predation of this voracious predator on young of the herbivorous cladoceran, M. micrura. Our findings stand opposite to the current theoretical framework where lead biomagnification occurs only in lower trophic levels.     

Determination of essential elements (copper,manganese, selenium and zinc) in fish and shellfish samples. Risk and nutritional assessment and mercury–selenium balance

Fish and shellfish are an important source not only of toxic heavy metals, but also of essential elements in the diet. In this study, levels of Cu, Mn, Se and Zn have been determined in fresh, canned and frozen fish and shellfish products. A total of 485 samples of the 43 most frequently consumed fish and shellfish species in Andalusia (Southern Spain) were analyzed for essential elements content. The potential human health risks for the consumers and the nutritional value of the products analyzed were assessed. Furthermore, the mercury-selenium ratios and the selenium health benefit value (Se-HBVs) were calculated. The highest concentrations of Cu were found in crustaceans species (shrimp and prawn) as they have hemocyanin (a copper-containing protein) that functions as an oxygen–transport molecule. Mn levels were higher in canned bivalve molluscs, such as cockle and clam, and in fresh common sole. Concerning Se, two fresh predatory fish species (tuna and swordfish) presented the most remarkable concentrations of this element. The highest concentration of the essential metals analysed was found for Zn, especially in fresh and canned mussels. All the species analyzed showed beneficial Hg:Se ratios and Se-HBVs, except for the shark species (blue shark and cat shark) and gilt-head bream because of their high Hg levels and low Se content, respectively. Nevertheless, the biomagnification usually observed in hazardous metals such as Hg would not occur for the essential elements measured in predatory species. The estimated daily intakes of the elements studied represented very low percentages of their reference values, ranging from 0.1% (Se) to 3.9% (Cu) for person weighting 60 kg, so the intake of these elements through fish and shellfish would not pose any risk for the average consumer. Moreover, the contribution of fish and shellfish products to the recommended daily allowances and adequate intakes of these mineral elements ranges from 2.5% (Mn) to 25.4% (Se).     

Mercury and other heavy metals in free-ranging mink of the lower Great Lakes basin, Canada, 1998–2006

Mercury concentrations were examined in livers of free-ranging mink (Neovison vison) trapped in the lower Great Lakes basin from 1998 to 2006. Significant geographic variation in total mercury levels was found in mink from 13 Great Lakes locations, many of which are within Great Lakes Areas of Concern (AOCs). Total mercury levels in mink from these locations were generally low to moderate, with means (±SE) ranging from 0.99 (±0.36) μg/g dry weight in mink from inland Lake Erie to 7.31 (±1.52) μg/g in mink from Walpole Island in the St. Clair River AOC. Overall, mercury exposure was highest in mink trapped in locations associated with large riverine wetlands. Total mercury concentrations were negatively related to the percentage of mercury present as methylmercury and positively related to selenium concentrations, consistent with increasing demethylation of methylmercury with increasing total mercury concentrations. One-year old mink had significantly higher levels of mercury and selenium than mink under 1 year but similar to mink 2 years of age and older. Mercury levels were below those associated with mercury toxicity. Concentrations of cadmium, lead and arsenic were low and largely associated with environmental background levels. Significant age and sex effects were found for cadmium. Lead levels were significantly lower in mink infected by the lung nematode parasite compared to uninfected animals. Further studies of biomagnification of methylmercury in wetland environments, where top predators such as mink may be an increased risk of exposure, are warranted.     

Is hepatic cytochrome P4501A1 expression predictive of hepatic burdens of dioxins, furans, and PCBs in Atlantic tomcod from the Hudson River estuary?

Hepatic cytochrome P4501A1 (CYP1A1) expression in fishes is frequently used to evaluate bioavailable aromatic hydrocarbon contamination of aquatic ecosystems. In controlled laboratory experiments, CYP1A1 expression in na?ve fishes is usually dose-responsive to aromatic hydrocarbons and in field studies levels of gene expression in natural populations often correspond with known levels of sediment-borne contaminants. We quantified CYP1A1 mRNA levels in juvenile Atlantic tomcod Microgadus tomcod from 42 sites in the Hudson River estuary to evaluate the correspondence between hepatic CYP1A1 expression and hepatic concentrations of persistent halogenated aromatic hydrocarbons and to determine the utility of CYP1A1 expression as a biomarker in evaluating the microgeographic distribution of bioavailable contaminants within a large aquatic ecosystem. We found significant spatial heterogeneity in CYP1A1 mRNA levels among collection sites with levels of gene expression differing in some cases by 23-34 folds. CYP1A1 mRNA expression was highest in tomcod from the Newark Bay complex and lowest in tomcod from the most upriver collection sites in the main stem of the Hudson River. Although levels of PCDDs, PCDFs, and PCBs expressed as TCDD TEQs and CYP1A1 mRNA were highest in tomcod from the Newark Bay complex, there was no relationship between hepatic halogenated aromatic hydrocarbon levels and hepatic CYP1A1 mRNA in tomcod from sites in the main stem of the Hudson River. These results suggest that levels of CYP1A1 expression in fish from sites highly polluted with mixtures of halogenated aromatic hydrocarbons and other xenobiotics may not always be reflective of levels of bioavailable aromatic hydrocarbon contaminants. Based on these results and earlier controlled laboratory experiments, we hypothesize that elevated levels of CYP1A1 expression in tomcod from the Hudson River may be due primarily to PAHs or other contaminants not measured in this study.     

Prevalence and associated demographic characteristics of exposure to multiple metals and their species in human populations: The United States NHANES, 2007–2012

Lead (Pb), cadmium (Cd), mercury (Hg), and arsenic (As) are among the top 10 pollutants of global health concern. Studies have shown that exposures to these metals produce severe adverse effects. However, the mechanisms underlying these effects, particularly joint toxicities, are poorly understood in humans. The objective of this investigation was to identify and characterize prevalent combinations of these metals and their species in the U.S. NHANES population to provide background data for future studies of potential metal interactions. Exposure was defined as urine or blood levels ≥ medians of the NHANES 2007–2012 participants ≥6 years (n = 7408). Adjusted-odds ratios (adj-OR) and 95% confidence intervals were determined for covariates (age, gender, and race/ethnicity, cotinine and body mass index). Species-specific analysis was also conducted for As and Hg including iAs (urinary arsenous acid and/or arsenic acid), met-iAs (urinary monomethylarsonic acid and/or dimethylarsinic acid), and oHg (blood methyl-mercury and/or ethyl-mercury). For combinations of As and Hg species, age- and gender-specific prevalence was determined among NHANES 2011–2012 participants (n = 2342). Data showed that approximately 49.3% of the population contained a combination of three or more metals. The most prevalent unique specific combinations were Pb/Cd/Hg/As, Pb/Cd/Hg, and Pb/Cd. Age was consistently associated with these combinations: adj-ORs ranged from 10.9 (Pb/Cd) to 11.2 (Pb/Cd/Hg/As). Race/ethnicity was significant for Pb/Cd/Hg/As. Among women of reproductive age, frequency of oHg/iAs/met-iAS and oHg/met-iAs was 22.9 and 40.3%, respectively. These findings may help prioritize efforts to assess joint toxicities and their impact on public health.     

Effects of formulation and route of administration on the systemic availability of Ex-RAD®, a new radioprotectant, in preclinical species

ON 01210.Na (Ex‐RAD^®) is a novel small molecule under development by Onconova Therapeutics, Inc. as a radiation protection agent. The purpose of this investigation was to evaluate the effect of various formulation approaches on the systemic exposure of ON 01210.Na. In vitro experiments were used to characterize the plasma binding and metabolic stability of ON 01210.Na using hepatocytes from several animal species (mouse, rat, rabbit, dog, monkey and human). In vivo studies were performed in rats, rabbits, dogs and monkeys, and involved several routes of administration (intravenous, subcutaneous, oral). Plasma protein binding was high across species (>83%), and the rate of ON 01210.Na metabolism was highest in rat and mouse hepatocytes. After intravenous administration, ON 01210.Na demonstrated biphasic elimination from the plasma. Systemic exposure parameters (C_max, AUC) were dose‐proportional up to 100 mg/kg. Following subcutaneous dosing, ON 01210.Na showed relatively low bioavailability upon administration of the suspension formulation. Developing a solution formulation significantly increased the bioavailability of the drug. This solution formulation demonstrated significant oral bioavailability in rabbit (70%) and monkey (30%). The findings from these preclinical studies provide an overview of the systemic disposition of ON 01210.Na, aiding in the development of optimal formulations and routes of administration for pivotal animal efficacy and clinical safety studies. A solution formulation of ON 01210.Na for s.c. administration is being developed, in addition to an oral dosage form for potential use of the compound as a radioprotectant and a radiation‐mitigating agent in wider military and civilian populations. Copyright © 2011 John Wiley & Sons, Ltd.     

Distribution of butyltins (TBT, DBT, MBT) in sediments of Gulf of Cádiz (Spain) and its bioaccumulation in the clam Ruditapes philippinarum

Surface sediment samples were analyzed for organotins namely tributyltin (TBT), dibutyltin and monobutyltin from six areas located in the Gulf of Cádiz (14 stations), Spain. The total butyltin ranged between undetected and 1,580 ng Sn g⁻¹. TBT generally prevailed in most of the samples, suggesting fresh inputs of butyltin compounds and/or less degradation of TBT. The observed levels of butyltins at several sites are much higher than that required to induce toxic effect on marine organisms, suggesting that these sediments are polluted with butyltin compounds. The clam Ruditapes philippinarum was used for studying bioaccumulation of butyltins by exposing them to contaminated sediments from the Gulf of Cádiz over a period of 28 days under laboratory conditions. Biota-sediment accumulation factor (BSAF) ranged from 0.44 to 3.99.     

Quantitative analysis of acylated oleanane-type triterpene saponins, chakasaponins I–III and floratheasaponins A–F, in the flower buds of Camellia sinensis from different regional origins

A quantitative analytical method was developed for the determination of acylated oleanane-type triterpene saponins, chakasaponins I-III (1-3) and floratheasaponins A-F (4-9), found in Camellia sinensis (Theaceae). The practical conditions for separation and detection of these saponins were established on an ODS column with methanol containing 5?mM trifluoroacetic acid as a mobile phase, and the detection and quantitation limits of the method were estimated to be 1.1-3.8 and 3.5-12.5?ng, respectively. The relative standard deviation values of intra- and interday precision were lower than 2.35 and 6.12%, respectively, overall mean recoveries of all saponins being 94.7-108.8%, and the correlation coefficients of all the calibration curves showed good linearity within the test ranges. To approve the validity of the protocol, extracts of 13 kinds of C. sinensis collected in China, Taiwan, Japan, and India were evaluated. The results indicated that the assay was reproducible and precise, and could be readily utilized for the quality evaluation of tea flowers. It was noteworthy that the distinct regional difference was observed with respect to the content of chakasaponins and floratheasaponins, more chakasaponins being contained in the extracts of tea flowers from Fujian and Sichuan provinces, China than those from Japan, Taiwan, and India. Optimum conditions for the extraction process were also established.     

Seasonality effects on the metal concentration and biochemical changes in Astyanax lacustris (Teleostei: Characiformes) from Doce River after the collapse of the Fundão dam in Mariana,Brazil

This study aimed to evaluate the harmful effects of metal accumulation on Astyanax lacustris and their biochemical response when exposed to the metals contained in the Doce River water, Brazil. The study was carried out in the Baixo Guandu region of the Doce River, Espírito Santo state. Samples were collected during the dry and wet seasons. Biochemical alterations were observed in the liver of A. lacustris, with apparent seasonal effects directly related to the high concentration of Al and Fe in this tissue. Despite this, the bioconcentration of metals in the organisms showed seasonal effects only in the gills, as they are the first organ in contact with the contaminated water. The data generated in this study provide an overview of the health of the ecosystem in this region, highlighting the harmful biochemical and metal concentration effects on the population of A. lacustris affected by the Fundão dam failure.     

Effects of perfluorooctanoic acid (PFOA) on the thyroid status,vitellogenin, and oxidant–antioxidant balance in the Murray River rainbowfish

Ecotoxicology - Perfluorooctanoic acid’s (PFOA) widespread use, presence and persistence in the aquatic environment has led to an increasing number of studies focusing on its toxicological...     

Concentrations and human health implications of heavy metals in wild aquatic organisms captured from the core area of Daya Bay’s Fishery Resource Reserve,South China Sea

Heavy metal concentrations in edible organisms from the core area of Daya Bay’s Fishery Resource Reserve, South China Sea, were determined. Samples of 14 crustacean, fish, and shellfish species were collected and analyzed. The As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn concentrations were 0.18–1.16, 0.002–0.919, 0.40–2.85, 0.07–4.10, 0.004–0.055, 0.14–1.19, 0.014–0.070, and 4.57–15.94 μg/g wet weight, respectively. The As concentrations were higher than the Chinese maximum permissible levels in all of the fish and shellfish species and two crustacean species, indicating that consumption of these wild species by humans may pose health risks. However, calculations of the health risks posed to humans indicated that no significant adverse health effects would be associated with consuming these species.     

Miroestrol, a phytoestrogen from Pueraria mirifica, improves the antioxidation state in the livers and uteri of β-naphthoflavone-treated mice

Oxidative stress is involved in the progression of several diseases such as diabetes, hypertension, and age-related diseases. Miroestrol (MR) is a potent phytoestrogen from the tuberous root of Pueraria mirifica, a plant used in traditional Thai medicine that is claimed to have rejuvenating effects. In this study, the effects of MR on the antioxidation system, including anti-lipid peroxidation; on the activities of superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase; and on glutathione content in the livers and uteri of β-naphthoflavone (BNF)-treated mice were determined. BNF-treated mice are a model of procarcinogen-exposed mice. The results showed that MR improved the antioxidant activities of SOD and CAT in the livers and uteri of both normal and BNF-treated mice, while estradiol (E2) increased SOD activity in the uteri of normal mice and CAT activity in the livers of both normal and BNF-treated mice. In the liver, MR increased the levels of several forms of glutathione, whereas in the uteri E2 and MR reduced the level of lipid peroxidation by decreasing the level of malondialdehyde. Therefore, the use of MR as an alternative hormone replacement therapy might be beneficial due to its ability to improve antioxidation systems.