Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.     

A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species

Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue⁻¹ with a global mean of 8.8 ± 0.9 μg g⁻¹. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g⁻¹). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g⁻¹) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g⁻¹). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed.     

An Assessment of the Ecological Condition of Long Island Sound, 1990–1993

Data from the Environmental Protection Agency's (EPA) Environmental Monitoring and Assessment Program (EMAP) from 1990 to 1993 were used to assess the condition of the Long Island Sound (LIS) estuary. Ambient water, sediment and biota were collected during the summer months from 53 LIS stations using an unbiased sampling design. The design consists of two LIS subunits, LIS proper, and small estuaries (<2.6 km2) at the margins of the Sound. Selected indicators of condition included: benthic species composition, abundance and biomass; fish species composition and gross external pathology; sediment physical and chemical characterization and sediment toxicity; and water clarity and quality. Results of the four-year sampling indicated that 28(±11)% of the areal extent of LIS proper had a benthic index < zero (impacted) and 51(±12)% of the area of small estuaries was impacted. Analysis of the results of other indicators also shows that small estuaries were particularly affected. For example, 42(±10)% of the areal extent of small estuaries exhibited sediment toxicity, and significant chemical contamination was evident in 22% of the area of small estuaries. Low dissolved oxygen (D.O.) concentrations (<5 ppm), however, appeared to affect only the deeper open waters of western LIS. Approximately 48(±12)% of the areal extent of LIS proper documented exposure to at least moderate D.O. stress (<5 ppm). The overall results of this monitoring study indicate that significant anthropogenic impacts have occurred in LIS and that if remediation was to take place, specific localized sediment problems would need attention. Point source and non-point source nutrient inputs to the Sound, which are believed to be the primary causative factor for the observed hypoxic conditions, would also need attention.     

Long-term seasonal changes of the Danube River eco-chemical status in the region of Serbia

Seasonal spatial and temporal changes of selected eco-chemical parameters in section of the Danube River flowing through Serbia were analyzed. Data for electrical conductivity (EC), dry and suspended matter, residue on ignition, chemical oxygen demand (COD), biochemical oxygen demand (BOD-5), ultraviolet extinction, dissolved oxygen (DO), oxygen saturation, pH, nitrates, total phosphorus, and nitrogen were collected between 1992 and 2006. The use of monthly medians combined with linear regression and two-sided t test has been proven to be the best approach for resolving trends from natural variability of investigated parameters and for determining trend significance. Patterns of temporal changes between different months were examined. It was also determined that spatial trends of some parameters oscillate in predictable manner, increasing in one part of the year and declining in the other. Regression slope coefficients, an excellent indicator for determining when the water quality is changing the most along the course of the Danube, reach their maximum during summer for temperature (t), electric conductivity, nitrates, and total N, while in the same season suspended matter, COD, BOD-5, DO, and oxygen saturation coefficients reach their minimum. Correlations for used data sets of selected parameters were analyzed for better understanding of their behavior and mutual relations. It was observed that as Danube flows through Serbia, its general eco-chemical status either stagnates or improves, but the rate of river self-purification often depends on the season of the year.     

Edaphic factors affecting the vertical distribution of radionuclides in the different soil types of Belgrade, Serbia

The specific activities of natural radionuclides ((40)K, (226)Ra and (232)Th) and Chernobyl-derived (137)Cs were measured in soil profiles representing typical soil types of Belgrade (Serbia): chernozems, fluvisols, humic gleysols, eutric cambisols, vertisols and gleyic fluvisols. The influence of soil properties and content of stable elements on radionuclide distribution down the soil profiles (at 5 cm intervals up to 50 cm depth) was analysed. Correlation analysis identified associations of (40)K, (226)Ra and (137)Cs with fine-grained soil fractions. Significant positive correlations were found between (137)Cs specific activity and both organic matter content and cation exchange capacity. Saturated hydraulic conductivity and specific electrical conductivity were also positively correlated with the specific activity of (137)Cs. The strong positive correlations between (226)Ra and (232)Th specific activities and Fe and Mn indicate an association with oxides of these elements in soil. The correlations observed between (40)K and Cr, Ni, Pb and Zn and also between (137)Cs and Cd, Cr, Pb and Zn could be attributed to their common affinity for clay minerals. These results provide insight into the main factors that affect radionuclide migration in the soil, which contributes to knowledge about radionuclide behaviour in the environment and factors governing their mobility within terrestrial ecosystems.     

Cumulative influences of a small city and former mining activities on the sediment quality of a subtropical estuarine protected area

This study aimed to evaluate the sediment quality in the estuarine protected area known as Cananéia-Iguape-Peruíbe (CIP-PA), located on the southeastern coast of Brazil. The study was designed considering possible negative effects induced by the city of Cananéia on the sediment quality of surrounding areas. This evaluation was performed using chemical and ecotoxicological analyses. Sediments were predominantly sandy, with low CaCO₃ contents. Amounts of organic matter varied, but higher contents occurred closer to the city, as well as did Fe and Total Recoverable Oils and Greases (TROGs) concentrations. Contamination by Cd and Cu was revealed in some samples, while concentrations of Zn were considered low. Chronic toxicity was detected in all tested sediments and acute toxicity occurred only in sediments collected near the city. The principal component analysis (PCA) revealed an association among Cd, Cu, Fe, TROG, fines, organic matter, CaCO₃, and chronic toxicity, whereas acute toxicity was found to be associated with Zn and mud. However, because Zn levels were low, acute toxicity was likely due to a contaminant that was not measured. Results show that there is a broad area within the CIP-PA that is under the influence of mining activities (chronic toxicity, moderate contamination by metals), whereas poorer conditions occur closer to Cananéia (acute toxicity); thus, the urban area seems to constitute a relevant source of contaminants for the estuarine complex. These results show that contamination is already capable of producing risks for the local aquatic biota, which suggests that the CIP-PA effectiveness in protecting estuarine biota may be threatened.     

Identification of the Meteorological Variables Influencing Evapotranspiration Variability Over Florida

Environmental Modeling & Assessment - Evapotranspiration (ET) plays an important role in agricultural water management and crop modeling. The highest mean annual ET values (889–1016 mm)...     

The responses of the hepatosomatic index (HSI), 7-ethoxyresorufin-O-deethylase (EROD) activity and glutathione-S-transferase (GST) activity in sea bass (Dicentrarchus labrax, Linnaeus 1758) caged at a polluted site: implications for their use in environmental risk assessment

The present study investigates the response of three hepatic biomarkers in adult sea bass (Dicentrarchus labrax, Linnaeus 1758) caged at a wastewater outlet of an oil refinery with fish caged at a pristine site used as controls. The biomarkers that were investigated were the hepatosomatic index (HSI), 7-ethoxyresorufin-O-deethylase (EROD) activity and glutathione-S-transferase (GST) activity. In addition, we have measured the levels of polycyclic aromatic hydrocarbons (PAHs) and selected heavy metals (lead, cadmium, mercury, copper and zinc) in sediment samples at the polluted site. Although the polluted site had high environmental levels of PAHs and heavy metals, there was no difference in hepatic EROD activity and HSI between fish caged at the polluted site and controls. On the other hand, GST activity was significantly lower in fish caged at the polluted site compared to controls. Our results point out that the studied biomarkers have limited use in environmental risk assessment studies, at least when caged adult sea bass is used as the sentinel species and complex toxicant mixtures are involved.