Metal equilibration in laboratory-contaminated (spiked) sediments used for the development of whole-sediment toxicity tests

The equilibration and bioavailability of metals in laboratory-contaminated sediments have been investigated in order to provide better guidance on acceptable procedures for spiking sediments with metals for use in the development of whole-sediment toxicity tests. The equilibration rates of Cd, Cu, Ni and Zn spiked into three estuarine surface sediments with varying properties were investigated. Changes to sediment pH, redox potential, porewater and acid-soluble metals, acid-volatile sulfide and bacterial activity during equilibration, effects of temperature and disturbances following equilibration are reported. The addition of metals to sediments caused major decreases in pH and increases in redox potential as metals displaced iron(II) into the porewaters and added metals and iron (following oxidation) were hydrolyzed. The rates of equilibration of metals in porewaters varied considerably and were dependent on sediment and metal properties. For the oxic/sub-oxic sediments studied, metal-spikes of Cd, Cu, Ni and Zn appeared near equilibrium after 25-45, 10-15, 30-70 and 20-40 days, respectively. Acid-soluble metal concentrations decreased during the equilibration period indicating that the metals become more strongly associated with the sediments with time (less bioavailable). Bacterial activity was greatest in the sediment equilibrated at pH 7 and decreased following the addition of metals. During the equilibration period, bacterial activity increased in sediments equilibrated at pH 6, remained low in sediments at pH 8 and varied erratically in sediments at pH 7. Spiked sediments were shown to equilibrate more slowly at lower temperatures resulting in high porewater metal concentrations. Disturbances to equilibrated sediments because of sample manipulation caused significant iron(II) oxidation and losses of metals from porewaters. The importance of documenting spiking and equilibration procedures and carefully measuring and reporting sediment parameters is highlighted so that contaminant bioavailability and exposure pathways can be interpreted and organism sensitivity accurately determined. Recommendations are given for the preparation of metal-spiked sediments for toxicity testing purposes.     

Change in Fish Fauna as Indication of Aquatic Ecosystem Condition in Río Grande de Morelia–Lago de Cuitzeo Basin, Mexico

Chirostoma charari and C. compressum, and they are presumed extinct. Twelve (63%) of the remaining species had declines in distribution. Sixteen (80%) of the 20 localities sampled had lost species. The greatest declines occurred in Lago de Cuitzeo proper and in the lower portion of the Río Grande de Morelia watershed. Species losses from the lake were attributable to drying and hypereutrophication of the lake because of substantial reductions in the amount and quality of tributary inputs, whereas losses from the Río Grande de Morelia watershed were the result of pollution from agricultural, municipal, and industrial sources, especially in the region around the city of Morelia. Three localities in the upper portion of the Río Grande de Morelia watershed—Cointzio reservoir, La Mintzita spring, and Insurgente Morelos stream—contained most of the remaining fish species diversity in the basin and deserve additional protection. Fish faunal changes indicated major declines in the health of aquatic ecosystems in the Morelia–Cuitzeo basin.     

Application of lead isotopic methods to the study of the anthropogenic lead provenance in Spanish overbank floodplain deposits

Changes in the principal sources of Pb in overbank sediment profiles have been documented for two Spanish areas by using Pb isotopes and Pb concentrations. These locations (Madrid and Tinto–Odiel basin) represent two of the most contaminated regions in Spain. The Community of Madrid is characterized by heavy industrial and urban activity, focused mainly in Madrid City. The Tinto–Odiel basin drains the Iberian Pyrite Belt, which hosts many polymetallic massive sulphides and is heavily affected by mining activities in their headwaters. It has been proven that the influence of anthropogenic activity is reflected in these overbank deposits by variations in Pb concentrations that, in general, correlate with shifts in the ²⁰⁶Pb/²⁰⁷Pb ratio. Rivas profile (downstream of Madrid) was found to be the most anthropogenically influenced site. The sediments within this profile which were recently deposited (170 ± 40 years BP) have the least radiogenic signatures. ²⁰⁶Pb/²⁰⁷Pb ratios ranged between 1.1763 and 1.1876 indicating significant contributions of anthropogenic Pb. In contrast, profiles upstream of Madrid possess an average ²⁰⁶Pb/²⁰⁷Pb ratio of 1.2272. It is difficult to clearly identify the most prominent source as the sediments appear to be characterized by an input from several sources. The floodplain profiles in the Tinto–Odiel basin exhibit uniform ²⁰⁶Pb/²⁰⁷Pb ratios ranging from 1.1627 (Odiel river) to 1.1665 (Tinto river). These ratios are similar to the ones possessed by sulphide ores in the area and differ from the ratios of other nonmineralized formations in the basin, indicating that mining activities are the primary, if not sole, source of Pb to the sediments.     

Ecological niche segregation among five toothed whale species off the NW Iberian Peninsula using ecological tracers as multi-approach

This study aims to assess niche segregation among the five main toothed whales that frequent the NW Iberian Peninsula waters: the common dolphin, the harbour porpoise, the bottlenose dolphin, the striped dolphin and the long-finned pilot whale. We used cadmium (Cd) and stable isotope ratios (δ¹³C and δ¹⁵N) as ecological tracers to assess degree of segregation in diet/trophic level and in foraging habitat, over various time-scales. δ¹³C values highlighted different habitats, while Cd concentrations highlighted feeding differences between oceanic and neritic species. Moreover, δ¹⁵N values suggest different trophic levels of prey targeted within oceanic and neritic species. Hence, results revealed long-term ecological segregation among five toothed whales that coexist in the NWIP and demonstrated the ability of ecological tracers to discriminate ecological niches among closely related species.     

Activity patterns and predatory behavior of an intertidal nemertean from rocky shores: Prosorhochmus nelsoni (Hoplonemertea) from the Southeast Pacific

Understanding the impact of environmental stressors on predator activity is a prerequisite to understanding the underlying mechanisms shaping community structure. The nemertean Prosorhochmus nelsoni is a common predator in the mid-intertidal zone on rocky shores along the Chilean coast, where it can reach very high abundances (up to 260 ind m⁻²) in algal turfs, algal crusts, barnacle crusts, and mixed substrata. Tidal and diurnal scans revealed that the activity of P. nelsoni is primarily restricted to night and early-morning low tides and is relatively low when air temperatures are high. On average, larger worms crawled faster than smaller worms, with their maximum velocity being influenced by substratum type. Their estimated rate of predation is 0.092 prey items nemertean⁻¹ day⁻¹, just below the laboratory rate of ~0.2 amphipods nemertean⁻¹ day⁻¹ previously estimated for this species. P. nelsoni consumes a diverse spectrum of prey items (i.e., amphipods, isopods, decapods, barnacles, and dipterans) and is possibly exerting a significant influence on its prey populations. We suggest that the opportunistic predatory behavior of this intertidal predator is caused by the trade-off between immediate persistence (e.g., avoidance of desiccation) and long-term survival through successful foraging.     

Influence of a dominant consumer species reverses at increased diversity

Theory and experiments indicate that changes in consumer diversity affect benthic community structure and ecosystem functioning. Although the effects of consumer diversity have been tested in the laboratory and the field, little is known about effects of consumer diversity in the subtidal zone, one of the largest marine habitats. We investigated the grazing effects of sea urchins on algal abundance and benthic community structure in a natural subtidal habitat of the Galápagos Islands. Three species of urchins (Eucidaris, Lytechinus, and Tripneustes) were manipulated in inclusion cages following a replacement design with three levels of species richness (one, two, and three species) with all possible two-species urchin combinations. Identity was the main factor accounting for changes in the percentage of substrate grazed and benthic community structure. Two out of the three two-species assemblages grazed more than expected, suggesting a richness effect, but analyses revealed that this increased grazing was due to a sampling effect of the largest and commercially valued urchin species, Tripneustes. Benthic community structure in treatments with Eucidaris, Lytechinus, and Tripneustes alone was significantly different at the end of the experiment, suggesting that resource use differentiation occurred. Communities in Tripneustes enclosures were characterized by abundant crustose coralline algae and grazed substrate, while those without it contained abundant green foliose algae (Ulva sp.). An unexpected emergent property of the system was that the most species-rich urchin assemblage underyielded, grazing less than any other assemblage with Tripneustes, effectively reversing its dominant influence observed in the two-species treatments. While further experiments are needed to discern the mechanisms of underyielding, it may be related to changing interspecific interactions as richness increases from two to three species or to density-dependent Tripneustes grazing. This study highlights the general importance of evaluating consumer richness effects across the entire range of species richness considered, as the performance of the most species-rich consumer assemblage could not be predicted by manipulations of intermediate levels of consumer species richness.     

Resource limitation of bacterial production distorts the temperature dependence of oceanic carbon cycling

Our view of the effects of temperature on bacterial carbon fluxes in the ocean has been confounded by the interplay of resource availability. Using an extensive compilation of cell-specific bacterial respiration (BRi) and production (BPi), we show that both physiological rates respond to changing temperature in a similar manner and follow the predictions of the metabolic theory of ecology. Their apparently different temperature dependence under warm, oligotrophic conditions is due to strong resource limitation of BP, but not of BRi. Thus, and despite previous preconception, bacterial growth efficiency (BGE = BPi/[BPi + BRi]) is not directly regulated by temperature, but by the availability of substrates for growth. We develop simple equations that can be used for the estimation of bacterial community metabolism from temperature, chlorophyll concentration, and bacterial abundance. Since bacteria are the greatest living planktonic biomass, our results challenge current understanding of how warming and shifts in ecosystem trophic state will modify oceanic carbon cycle feedbacks to climate change.     

Using lysosomal membrane stability of haemocytes in Ruditapes philippinarum as a biomarker of cellular stress to assess contamination by caffeine, ibuprofen, carbamazepine and novobiocin

Although pharmaceuticals have been detected in the environment only in the range from ng/L to g/L, it has been demonstrated that they can adversely affect the health status of aquatic organisms. Lysosomal membrane stability (LMS) has previously been applied as an indicator of cellular well-being to determine health status in bivalve mussels. The objective of this study is to evaluate LMS in Ruditapes philippinarum haemolymph using the neutral red retention assay (NRRA). Clams were exposed in laboratory conditions to caffeine (0.1, 5, 15, 50 μg/L), ibuprofen (0.1, 5, 10, 50 μg/L), carbamazepine and novobiocin (both at 0.1, 1, 10, 50 μg/L) for 35 days. Results show a dose-dependent effect of the pharmaceuticals. The neutral red retention time measured at the end of the bioassay was significantly reduced by 50% after exposure to environmental concentrations (p < 0.05) (caffeine = 15 μg/L; ibuprofen = 10 μg/L; carbamazepine = 1 μg/L and novobiocin = 1 μg/L), compared to controls. Clams exposed to these pharmaceuticals were considered to present a diminished health status (retention time < 45 min), significantly worse than controls (96 min) (p < 0.05). The predicted no environmental effect concentration (PNEC) results showed that these pharmaceuticals are very toxic at the environmental concentrations tested. Measurement of the alteration of LMS has been found to be a sensitive technique that enables evaluation of the health status of clams after exposure to pharmaceuticals under laboratory conditions, thus representing a robust Tier-1 screening biomarker.     

Electrochemical degradation of chlorophenoxy and chlorobenzoic herbicides in acidic aqueous medium by the peroxi-coagulation method

The degradation of 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as chlorophenoxy herbicides, as well as of 3,6-dichloro-2-methoxybenzoic acid (dicamba) as chlorobenzoic herbicide, has been studied by peroxi-coagulation. This electrochemical method yields a very effective depollution of all compounds in acidic aqueous medium of pH 3.0 working under pH regulation, since they are oxidized with hydroxyl radicals produced from Fenton's reaction between Fe(2+) and H(2)O(2) generated by the corresponding Fe anode and O(2)-diffusion cathode. Their products can then be removed by mineralization or coagulation with the Fe(OH)(3) precipitate formed. Both degradative paths compete at low currents, but coagulation predominates at high currents. The peroxi-coagulation process of dicamba at I>or=300 mA leads to more than 90% of coagulation, being much more efficient than its comparative electro-Fenton treatment with a Pt anode and 1 mM Fe(2+), where only mineralization takes place. For the chlorophenoxy compounds, electro-Fenton gives a slightly lower depollution than peroxi-coagulation, because more easily oxidable products are produced. Oxidation of chlorinated products during peroxi-coagulation is accompanied by the release of chloride ion to the solution. The efficiency of this method decreases with increasing electrolysis time and current. The decay of all herbicides follows a pseudo-first-order reaction, with a similar constant rate for 4-CPA, MCPA, 2,4-D and 2,4,5-T, and a higher value for dicamba.