Tipping Elements in the Arctic Marine Ecosystem

The Arctic marine ecosystem contains multiple elements that present alternative states. The most obvious of which is an Arctic Ocean largely covered by an ice sheet in summer versus one largely devoid of such cover. Ecosystems under pressure typically shift between such alternative states in an abrupt, rather than smooth manner, with the level of forcing required for shifting this status termed threshold or tipping point. Loss of Arctic ice due to anthropogenic climate change is accelerating, with the extent of Arctic sea ice displaying increased variance at present, a leading indicator of the proximity of a possible tipping point. Reduced ice extent is expected, in turn, to trigger a number of additional tipping elements, physical, chemical, and biological, in motion, with potentially large impacts on the Arctic marine ecosystem.     

Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

Organochlorine contaminants in different tissues from Platichthys flesus (Pisces,Pleuronectidea)

Polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) are organic contaminants that tend to accumulate in fish. Estuaries are exposed to high anthropogenic activities, therefore tending to accumulate more contaminants than the adjacent coastal waters. Platichthys flesus, a fish with high economic value, was analysed for PCBs and HCB along its different age groups, in liver, gills, gonads and muscle. Younger fishes were caught in the estuary, whereas older fishes were caught in the adjacent coastal waters and acquired at Figueira da Foz Regional Office of Docapesca-Portos e Lotas, SA. Both contaminants concentrations follow the pattern: liver > gills > muscle. Hepatosomatic index had the lowest values in younger fishes and the highest values in older fishes. Condition factor values remain stable with age. Younger fishes had higher PCBs concentrations than the older fishes. In opposition HCB was only detected in fish from 3+ to 5+ and its concentration tended to increase with age. Overall P. flesus is considered safe for human intake.     

Mercury bioaccumulation and decontamination kinetics in the edible cockle Cerastoderma edule

Mercury bioaccumulation and decontamination kinetics in the edible cockle Cerastoderma edule were studied through a mesocosms experiment after a medium-term exposure to the metal.The results revealed that the bivalve presented distinct bioaccumulation kinetics according to the different tissues. While the gills showed a linear accumulation pattern, the digestive gland and the entire organism presented a saturation model, with higher accumulation during the first 7d of exposure and lower during the rest of the time. In addition, the bioaccumulation rate was not proportional to the Hg concentration, since the organisms under lower contamination presented higher bioconcentration factors than the ones under higher contamination. Gills were the tissues with higher mercury accumulation capability.Concerning the decontamination phase, C. edule lost approximately 80% of the mercury after 24 h exposure in clean seawater. Nevertheless, never reached the original condition, showing in the final (20 d detox), Hg levels (>0.5 ppm) higher than those allowed by the legislation regulating human food consumption. This represents a matter of concern for Human health.     

Sources of potentially toxic elements and organic pollutants in an urban area subjected to an industrial impact

Urban and industrial development has caused a major impact on environmental soil quality. This work assesses the extent and severity of contamination in a small urban area subjected to an industrial impact and identifies the major anthropogenic inputs. Twenty-six soil samples were collected from agricultural and urban sites, and concentrations of potentially toxic elements (As, Cd, Cu, Cr, Fe, Mn, Ni, Pb and Zn), PAHs and PCBs, were determined. In spite of the low median concentrations observed, some sites represent a potential hazard for human health and ecosystems. Concentrations of contaminants were higher than those found in a nearby city, indicating that the study area is affected by the surrounding industry. The use of multivariate statistical analyses allowed for the identification of the main factors controlling the variability of potentially toxic elements and organic pollutants in the soils. The presence of Cr, Fe, Mn and Ni was associated with geogenic inputs, and Cu, Pb, Zn, As, PAHs and PCBs were associated with anthropogenic inputs. Industry and traffic were the most important anthropogenic sources. Soil characteristics were identified as important factors controlling the spatial variability of elements, both from recognised natural and anthropogenic origin. Differences between land uses were observed, which may be attributed to both management practices and proximity to sources.     

Major inputs and mobility of potentially toxic elements contamination in urban areas

Soil quality in urban areas is affected by anthropogenic activities, posing a risk to human health and ecosystems. Since the pseudo-total concentrations of potentially toxic elements may not reflect their potential risks, the study of element mobility is very important on a risk assessment basis. This study aims at characterising the distribution and major sources of 34 elements in two Portuguese urban areas (Lisbon and Viseu), with different geological characteristics, industrial and urban development processes. Furthermore, the potential availability of As, Co, Cr, Cu, Ni, Pb and Zn was assessed, by measuring the fraction easily mobilised. Lisbon is enriched in elements of geogenic and anthropogenic origin, whereas in the smaller city, the high levels observed are mainly related to a geogenic origin. Background values can be more relevant than the dimension of the city, even when anthropogenic components may be present, and this parameter should be considered when comparing results from different cities. Regarding the potential available fraction, a high variability of results was observed for elements and for sampling sites with an influence of the soil’s general characteristics. Elements showing very high concentrations due to geological reasons presented, in general, a low mobility and it was not dependent on the degree of contamination. For elements with major anthropogenic origin, only Zn was dependent on the pseudo-total content. Yet, the highest available fractions of some elements, both with major geogenic and anthropogenic origin, were observed in specific contaminated samples. Therefore, a site-specific evaluation in urban soils is important due to the high spatial variability and heterogeneity.     

Trace level determination of selected organophosphorus pesticides and their degradation products in environmental air samples by liquid chromatography-positive ion electrospray tandem mass spectrometry

This paper describes a new analytical method for determination of organophosphorus pesticides (OPs) along with their degradation products involving liquid chromatography (LC) positive ion electrospray (ESI+) tandem mass spectrometry (MS-MS) with selective reaction monitoring (SRM). Chromatography was performed on a Gemini C6-Phenyl (150 mmx2.0 mm, 3 microm) with a gradient elution using water-methanol with 0.1% formic acid, 2 mM ammonium acetate mobile phase at a flow rate of 0.2 mL min(-1). The LC separation and MS/MS operating conditions were optimized with a total analysis time less than 40 minutes. Method detection limits of 0.1-5 microg L(-1) for selected organophosphorus pesticides (OP), OP oxon degradation products, and other degradation products: 3,5,6-trichloro-2-pyridinol (TCP); 2-isopropyl-6-methyl-4-pyrimidol (IMP); and diethyl phosphate (DEP). Some OPs such as fenchlorphos are less sensitive (MDL 30 microg L(-1)). Calibration curves were linear with coefficients of correlation better than 0.995. A three-point identification approach was adopted with area from first selective reaction monitoring (SRM) transition used for quantitative analysis, while a second SRM transition along with the ratio of areas obtained from the first to second transition are used for confirmation with sample tolerance established by the relative standard deviation of the ratio obtained from standards. This new method permitted the first known detection of OP oxon degradation products including chlorpyrifos oxon at Bratt's Lake, SK and diazinon oxon and malathion oxon at Abbotsford, BC in atmospheric samples. Atmospheric detection limits typically ranged from 0.2-10 pg m(-3).     

Correlates of bushmeat in markets and depletion of wildlife

We used data on number of carcasses of wildlife species sold in 79 bushmeat markets in a region of Nigeria and Cameroon to assess whether species composition of a market could be explained by anthropogenic pressures and environmental variables around each market. More than 45 mammal species from 9 orders were traded across all markets; mostly ungulates and rodents. For each market, we determined median body mass, species diversity (game diversity), and taxa that were principal contributors to the total number of carcasses for sale (game dominance). Human population density in surrounding areas was significantly and negatively related to the percentage ungulates and primates sold in markets and significantly and positively related to the proportion of rodents. The proportion of carnivores sold was higher in markets with high human population densities. Proportion of small‐bodied mammals (<1 kg) sold in markets increased as human population density increased, but proportion of large‐bodied mammals (>10 kg) decreased as human population density increased. We calculated an index of game depletion (GDI) for each market from the sum of the total number of carcasses traded per annum and species, weighted by the intrinsic rate of natural increase (r_max) of each species, divided by individuals traded in a market. The GDI of a market increased as the proportion of fast‐reproducing species (highest r_max) increased and as the representation of species with lowest r_max (slow‐reproducing) decreased. The best explanatory factor for a market's GDI was anthropogenic pressure—road density, human settlements with >3000 inhabitants, and nonforest vegetation. High and low GDI were significantly differentiated by human density and human settlements with >3000 inhabitants. Our results provided empirical evidence that human activity is correlated with more depleted bushmeat faunas and can be used as a proxy to determine areas in need of conservation action.     

Pesticides in the surface waters of the Camanducaia River watershed,Brazil

Abstract

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4?mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57?μg L^?1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5?m y^?1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.