(Table 1) Geochemistry of Sapropels of the Mediterranean Sea

Sapropels -organic-matter rich layers- are common in Neogene sediments of the eastern Mediterranean Sea. The formation of these layers has been attributed to climate-related increases in organic-matter production (Calvert et al., 1992, doi:10.1038/359223a0; Rossignol-Strick et al., 1982, doi:10.1038/295105a0; Rohling, 1994, doi:10.1016/0025-3227(94)90202-X) and increased organic-matter preservation due to oxygen depletion in more stagnant bottom waters (Rossignol-Strick et al., 1982, doi:10.1038/295105a0; Rohling, 1994, doi:10.1016/0025-3227(94)90202-X). Here we report that eastern Mediterranean Pliocene sapropels (Emeis et al., 1996, doi:10.2973/odp.proc.ir.160.102.1996) contain molecular fossils of a compound (isorenieratene) known to be synthesized by photosynthetic green sulphur bacteria, suggesting that sulphidic (euxinic) -and therefore anoxic- conditions prevailed in the photic zone of the water column. These sapropels also have a high trace-metal content, which is probably due to the efficient scavenging of these metals by precipitating sulphides in a euxinic water column. The abundance and sulphur-isotope composition of pyrite are consistent with iron sulphide formation in the water column. We conclude that basin-wide water-column euxinia occurred over substantial periods during Pliocene sapropel formation in the eastern Mediterranean Sea, and that the ultimate degradation of the increased organic-matter production was strongly influential in generating and sustaining the euxinic conditions.

Seawater carbonate chemistry and community metabolism during an experiment with a coral reef, 2003

The effect of elevated pCO2 on the metabolism of a coral reef community dominated by macroalgae has been investigated utilizing the large 2650 m3 coral reef mesocosm at the Biosphere-2 facility near Tucson, Arizona. The carbonate chemistry of the water was manipulated to simulate present-day and a doubled CO2 future condition. Each experiment consisted of a 1-2 month preconditioning period followed by a 7-9 day observational period. The pCO2 was 404 ± 63 ?atm during the present-day pCO2 experiment and 658 ± 59 ?atm during the elevated pCO2 experiment. Nutrient levels were low and typical of natural reefs waters (NO3? 0.5-0.9 ?M, NH4+ 0.4 ?M, PO43? 0.07-0.09 ?M). The temperature and salinity of the water were held constant at 26.5 ± 0.2°C and 34.4 ± 0.2 ppt. Photosynthetically available irradiance was 10 ± 2 during the present-day experiment and 7.4 ± 0.5 mol photons m?2 d?1 during the elevated pCO2 experiment. The primary producer biomass in the mesocosm was dominated by four species of macroalgae; Haptilon cubense, Amphiroa fragillisima, Gelidiopsis intricata and Chondria dasyphylla. Algal biomass was 10.4 mol C m?2 during the present-day and 8.7 mol C m?2 and during the elevated pCO2 experiments. As previously observed, the increase in pCO2 resulted in a decrease in calcification from 0.041 ± 0.007 to 0.006 ± 0.003 mol CaCO3 m?2 d?1. Net community production (NCP) and dark respiration did not change in response to elevated pCO2. Light respiration measured by a new radiocarbon isotope dilution method exceeded dark respiration by a factor of 1.2 ± 0.3 to 2.1 ± 0.4 on a daily basis and by 2.2 ± 0.6 to 3.9 ± 0.8 on an hourly basis. The 1.8-fold increase with increasing pCO2 indicates that the enhanced respiration in the light was not due to photorespiration. Gross production (GPP) computed as the sum of NCP plus daily respiration (light + dark) increased significantly (0.24 ± 0.03 vs. 0.32 ± 0.04 mol C m?2 d?1). However, the conventional calculation of GPP based on the assumption that respiration in the light proceeds at the same rate as the dark underestimated the true rate of GPP by 41-100% and completely missed the increased rate of carbon cycling due to elevated pCO2. We conclude that under natural, undisturbed, nutrient-limited conditions elevated CO2 depresses calcification, stimulates the rate of turnover of organic carbon, particularly in the light, but has no effect on net organic production. The hypothesis that an increase pCO2 would produce an increase in net production that would counterbalance the effect of decreasing saturation state on calcification is not supported by these data.

Interannual and (multi-)decadal variability in the sedimentary BIT index of Lake Challa, East Africa, over the past 2200 years: assessment of the precipitation proxy

The branched vs. isoprenoid tetraether (BIT) index is based on the relative abundance of branched tetraether lipids (brGDGTs) and the isoprenoidal GDGT crenarchaeol. In Lake Challa sediments the BIT index has been applied as a proxy for local monsoon precipitation on the assumption that the primary source of brGDGTs is soil washed in from the lake's catchment. Since then, microbial production within the water column has been identified as the primary source of brGDGTs in Lake Challa sediments, meaning that either an alternative mechanism links BIT index variation with rainfall or that the proxy's application must be reconsidered. We investigated GDGT concentrations and BIT index variation in Lake Challa sediments at a decadal resolution over the past 2200 years, in combination with GDGT time-series data from 45 monthly sediment-trap samples and a chronosequence of profundal surface sediments.

Our 2200-year geochemical record reveals high-frequency variability in GDGT concentrations, and therefore in the BIT index, superimposed on distinct lower-frequency fluctuations at multi-decadal to century timescales. These changes in BIT index are correlated with changes in the concentration of crenarchaeol but not with those of the brGDGTs. A clue for understanding the indirect link between rainfall and crenarchaeol concentration (and thus thaumarchaeotal abundance) was provided by the observation that surface sediments collected in January 2010 show a distinct shift in GDGT composition relative to sediments collected in August 2007. This shift is associated with increased bulk flux of settling mineral particles with high Ti / Al ratios during March–April 2008, reflecting an event of unusually high detrital input to Lake Challa concurrent with intense precipitation at the onset of the principal rain season that year. Although brGDGT distributions in the settling material are initially unaffected, this soil-erosion event is succeeded by a massive dry-season diatom bloom in July–September 2008 and a concurrent increase in the flux of GDGT-0. Complete absence of crenarchaeol in settling particles during the austral summer following this bloom indicates that no Thaumarchaeota bloom developed at that time. We suggest that increased nutrient availability, derived from the eroded soil washed into the lake, caused the massive bloom of diatoms and that the higher concentrations of ammonium (formed from breakdown of this algal matter) resulted in a replacement of nitrifying Thaumarchaeota, which in typical years prosper during the austral summer, by nitrifying bacteria. The decomposing dead diatoms passing through the suboxic zone of the water column probably also formed a substrate for GDGT-0-producing archaea. Hence, through a cascade of events, intensive rainfall affects thaumarchaeotal abundance, resulting in high BIT index values.

Decade-scale BIT index fluctuations in Lake Challa sediments exactly match the timing of three known episodes of prolonged regional drought within the past 250 years. Additionally, the principal trends of inferred rainfall variability over the past two millennia are consistent with the hydroclimatic history of equatorial East Africa, as has been documented from other (but less well dated) regional lake records. We therefore propose that variation in GDGT production originating from the episodic recurrence of strong soil-erosion events, when integrated over (multi-)decadal and longer timescales, generates a stable positive relationship between the sedimentary BIT index and monsoon rainfall at Lake Challa. Application of this paleoprecipitation proxy at other sites requires ascertaining the local processes which affect the productivity of crenarchaeol by Thaumarchaeota and brGDGTs.

Employment of the Technique of Radiotracers for Analysis of Industrial Filters

The main aim of this work is to develop a methodology to evaluate the characteristics of porous media in filter using the radio-tracing technique. To do this, an experimental prototype filter made up of an acrylic cylinder, vertically mounted and supported on the lower side by a controlled leaking valve was developed. Two filters (spheres of acrylic and silica crystals) were used to check the movement of the water through the porous media using 123I in its MIBG (iodine-123-meta-iodo benzyl-guanidine) form. Further up the filter an instantaneous injection of the substance makes it possible to see the passage of radioactive clouds through the two scintillatory detectors NaI (2x2)” positioned before and immediately after the cylinder with the filtering element (porous media). The are caused by the detectors on the passage of the radioactive cloud are analyzed through statistical functions using the weighted moment method which makes it possible to calculate the Residence-Time (the amount of time the tracer takes to thoroughly pass through the filter) per the equation of dispersion in tubular flow and the one-directional flow of the radiotracer in the porous media.

Texture and composition of the Rosa Marina beach sands (Adriatic coast, southern Italy): a sedimentological/ecological approach

Beach sands from the Rosa Marina locality (Adriatic coast, southern Italy) were analysed mainly microscopically in order to trace the source areas of their lithoclastic and bioclastic components. The main cropping out sedimentary units were also studied with the objective to identify the potential source areas of lithoclasts. This allowed to establish how the various rock units contribute to the formation of beach sands. The analysis of the bioclastic components allows to estimate the actual role of organisms regarding the supply of this material to the beach. Identification of taxa that are present in the beach sands as shell fragments or other remains was carried out at the genus or family level. Ecologi- cal investigation of the same beach and the recognition of sub-environments (mainly distinguished on the basis of the nature of the substrate and of the water depth) was the key topic that allowed to establish the actual source areas of bioclasts in the Rosa Marina beach sands. The sedimentological analysis (including a physical study of the beach and the calculation of some statistical parameters concerning the grain-size curves) shows that the Rosa Marina beach is nowadays subject to erosion.

Effect of Urucu oil (Brazilian Amazon) on the biomass of the aquatic macrophyte Eichhornia crassipes (Mart.) Solms (Pontederiaceae)

Os rios e lagos de várzea da província petrolífera de Urucu, na Amazônia Central, são amplamente colonizados por macrófitas aquáticas, que podem ser afetadas por acidentes durante a exploração e o transporte de petróleo. Entre as macrófitas, a espécie flutuante Eichhornia crassipes (aguapé) ocorre abundantemente na região; OBJETIVO: O objetivo desse estudo foi verificar o efeito de diferentes dosagens do petróleo de Urucu (0; 0,5; 1,5 e 3,0 L.m-2) na biomassa viva e morta de E. crassipes e em algumas características físicas e químicas da água; MÉTODOS: O experimento teve oitenta e quatro dias de duração. A cada sete dias foi determinada a biomassa (viva e morta) de E. crassipes e os valores de temperatura, pH, condutividade elétrica e oxigênio dissolvido da água; RESULTADOS: A dosagem de 0,5 L.m-2 foi suficiente para causar mortalidade parcial (48%) em E. crassipes após trinta e cinco dias de exposição ao petróleo. A dosagem de 3,0 L.m-2 causou mortalidade total (100%) em E. crassipes em oitenta e quatro dias de exposição. A decomposição do petróleo e da biomassa morta de E. crassipes provocam a redução do oxigênio dissolvido e do pH, e aumento da condutividade elétrica e de fósforo total na água; CONCLUSÕES: Nós concluímos que um derramamento de petróleo pode provocar mortalidade total em uma população de uma espécie de macrófita, mas não em uma outra. Isto pode alterar a diversidade de espécies de macrófitas na região impactada. No caso de Eichhornia crassipes e Pistia stratiotes, um derramamento de petróleo de Urucu pode favorecer E. crassipes, a espécie menos sensível ao petróleo.

A Hydrogeologic Evaluation of the Waterloo Area in the Upper Jefferson River Valley, Montana

The Upper Jefferson River is one of the most dewatered rivers in Montana. The river exists in an intermontane basin filled with sediment transported from the Highland Mountains to the west, the Tobacco Root Mountains to the east, and the Jefferson River from the south. The Upper Jefferson River Valley is highly dependent on the Jefferson River as the main industry in the valley is agriculture. A majority of the valley is irrigated and used to grow crops, and a good portion is also used for cattle grazing. The residents of the Upper Jefferson River Valley use the aquifer as the main source of potable water. The Jefferson River is also widely used for recreation. This study took place in the Waterloo area of the Upper Jefferson River Valley, approximately 20 miles south of Whitehall, Montana. The Waterloo area provides significant groundwater base flow to the Jefferson River, which is particularly important during the late irrigation season when the river is severely dewatered, and elevated surface-water temperatures occur, creating irrigation water shortages and poor trout habitat. This area contains two springfed streams, Willow Springs and Parson’s Slough, which discharge to the Jefferson River providing cool water in the late season as well as providing the most important trout spawning habitat in the valley. The area is bordered on both the east and west by irrigation ditches, and about 60% of the study area is irrigated. Tile drains were installed in the study area in close proximity to Parsons Slough causing some concern by neighboring residents. This study evaluated relationships between surface water, groundwater, and irrigation practices so that water managers and others can make informed management decisions about the Upper Jefferson River. Data was collected via a network of groundwater wells and surface-water sites. Additionally, water-quality samples were taken and an aquifer test was conducted to determine aquifer properties. The field data were analyzed and a groundwater budget was created in order to evaluate the aquifer. Results of the groundwater budget show that seepage from the irrigation canals and irrigation recharge have the biggest influence on recharge of the aquifer. There is significant groundwater outflow from the aquifer in the spring-fed streams as well as discharge to the Jefferson River. In comparing previous study results to this study’s results, there is no evidence of the water table decreasing due to irrigation practice changes or tile drain installation. However, given the amount of recharge irrigation practices contribute to the aquifer, if significant changes were made, they may affect groundwater elevations. Also lining the irrigation ditches would have a significant impact on the aquifer, as the amount of seepage would be greatly reduced.

Feeding ecology of the deep-sea lanternshark Etmopterus pusillus (Elasmobranchii: Etmopteridae) in the northeast Atlantic

This study provides the first description of the feeding ecology of the smooth lanternshark Etmopterus pusillus based on stomach contents of specimens caught as bycatch in the Algarve (southern Portugal) with bottom trawling and bottom longline. The diet of E. pusillus consists mainly of fish (dry weight (% W)=87.1%; frequency of occurrence (%FO)=28.6%; number (%N)=30.3%), crustaceans (%W=7.7%; %FO=36.7%; %N=3.4%) and cephalopods (%W=4.7%; %FO=11.3%; %N=11.1%). The diet did not vary between sexes. Ontogenic changes were detected: crustaceans decreased in importance as the sharks increased in size and fish became dominant in the diet of adults. Combining two fishing methods provided broad information on the diet of E. pusillus, as bottom trawling caught smaller specimens and longlines caught larger individuals. E. pusillus feeds mainly on non-commercial species, and therefore does not compete directly with commercial fisheries. Finally, E. pusillus feeds in various parts of the water column and thus it can access a wide range of prey; however, this also means that it can be caught by both gears, making it more vulnerable in terms of conservation.

La production de thiols biogéniques par les microorganismes aquatiques

Les thiols à faible masse moléculaire (FMM) peuvent affecter la biodisponibilité du mercure et mener à une plus grande production de méthylmercure par les microorganismes méthylants. Les résultats d’une étude réalisée au sein de la matrice extracellulaire du périphyton de la zone littorale d’un lac des Laurentides ont démontré que les concentrations en thiols à FMM retrouvées dans cette matrice sont jusqu’à 1000 fois supérieures à celles de la colonne d’eau avoisinante. Ces thiols sont significativement corrélés à la chlorophylle a du périphyton, suggérant une production par les algues. Le mercure de la matrice extracellulaire, plus spécifiquement dans la fraction colloïdale mobile, est aussi corrélé aux thiols d’origine algale. Ces résultats suggèrent qu’une accumulation de thiols s’opère dans l’espace extracellulaire du périphyton et qu’ils peuvent favoriser le transfert du mercure vers les microorganismes produisant le méthylmercure. Les résultats d’une seconde étude menée sur les méthodes de préservation d’échantillons d’eau pour la conservation des thiols à FMM ont démontré que la température optimale d’entreposage était de -80 °C et que la lyophilisation menait à une sous-estimation des concentrations mesurées. Les taux de dégradation étaient plus rapides lors de la conservation à -20 °C et variables selon la chimie de l’eau utilisée et les espèces de thiols observées. Suivant ces résultats, nous proposons un cadre de recherche pour de futures études sur la spéciation du mercure dans le périphyton et nous suggérons des précautions lors de la manipulation et de la conservation des thiols à FMM d’échantillons naturels.

Análise dos fatores responsáveis pela alta salinidade do aqüífero fissural da microbacia da Riacho do Feijão - Pedro Avelino/RN

The fissures aquifer northeast semi-arid Brazilian, present high text frequently of leave, with of low a hídric availability. The research has as objective main to analyze the components that inside influence in the salinity of the waterbearing fissures of an evaluation physicist-chemistry of the water, leading in consideration the physical interventions of the environment. One used techniques of interpretation of image of Landsat satellite -1999 and delimitation of the micro basin through the topographical map SUDENE. One identified waters of the NaCl type with Ca++ and Mg++ in secondary concentrations. The analyzed wells (15), had presented an average salinity of 5.147 mg/L of STD and a well only supplies drinking waters with 319 mg/L of STD. The recharge of the aquifer one if carries through for infiltration in the open fracture of ortognaisse it migmatization. The type and directions of the fracture do not control the STD. Relations between salinity and out let do not exist. The quality of the well of low salinity is identical the superficial waters (aquifer dam and alluvial). The studies of the meteoric erosion processes had evidenced that in the transformations of the rock in ground, the Ca++ and Na+ are taken for superficial waters. The treatment of the data chemical showed that the grade of Na+, Ca++, Mg++ and Cl-are controlled for the evaporation process, from only water that would have the qualities of superficial waters or the well of low salinity. Already the HCO3-grade is controlled for the precipitation of the dolomite. The STD of this aquifer one would be consequence of the high tax of evaporation of dams constructed in regions of plain topography. You leave them precipitated in deep argillaceous ones dry dams are led for the aquifer in first rains. The research suggests some recommendations for the use and exploitation of the water salinity in piscicultura, carcinicultura, culture of the grass-salt (Atriplex sp), among others

Características físicas e químicas das águas superficiais e subterrâneas (nas proximidades do canal), dos ribeirões do Moquém e Água Clara (Médio Tietê Superior - SP), em função das variações hidrológicas

As teorias sobre o funcionamento dos sistemas lóticos evoluíram nos últimos anos, os condicionantes geológicos/geomorfológicos como também as regiões de transição têm recebido importância crescente. As regiões de transição merecem destaque uma vez que os sistemas lóticos estabelecem interações de fluxo com os ambientes vizinhos (atmosféricos, terrestres e subterrâneos) e a troca de materiais estabelecida entre esses sistemas é importante para a definição de suas características. As bacias hidrográficas dos ribeirões do Moquém e Água Clara, estudadas no presente trabalho, apresentam: proximidade geográfica além de semelhanças morfológicas e climáticas, porém diferem quanto aos aspectos geológicos e geomorfológicos. A partir desses aspectos, a presente pesquisa investigou as flutuações sazonais nas relações físicas, química e hidrológicas entre águas superficiais e subterrâneas (adjacências do canal), na região do baixo curso dos ribeirões já citados. Foram escolhidos dois trechos em cada ribeirão para a realização de: (1) inventário hidrológico mensal, a partir de medidas de velocidade de escoamento, vazão e do nível de água em poços instalados na região marginal dos rios nos trechos de estudo; (2) caracterização física e química de testemunhos da região marginal dos rios, onde foram utilizadas amostras obtidas durante a perfuração dos poços; (3) amostragens das águas superficiais subterrâneas no mesmo período do inventário para a determinação das características físicas e químicas das mesmas. Os resultados destacaram os seguintes itens. O fluxo de base garantiu vazões regulares e elevadas ao ribeirão Água Clara, ao mesmo tempo que as vazões foram quase insignificantes no ribeirão do Moquém, fato esse que apresenta importância ecológica. A química das águas dos ribeirões estudados é distinta, possivelmente, como resposta às características naturais das bacias. Nos dois trechos de estudo, as águas superficiais e subterrâneas apresentaram diferenças físicas e químicas, o que pode indicar que as trocas entre o canal do rio e suas adjacências são pequenas e/ou lentas. Com base nas observações desta pesquisa, recomenda-se que as características quantitativas e qualitativas, distintas, entre as águas dos ribeirões do Moquém e Água Clara devem ser avaliadas durante a tomada de decisões em processos de gestão de recursos hídricos.

Bioavailability and toxicity of chemicals in inland waters : the importance of prevailing water chemistry and implications for risk assessment

Physicochemical characterization of freshwater samples from Finland, Sweden, the Netherlands, and Spain revealed that water hardness and pH decreased and the quantity and quality of humic substances changed considerably in this geographical series from south to north. Since the ambient water chemistry may affect the availability of chemicals, the total aqueous concentration of a chemical may be insufficient to predict the bioconcentration, subsequent biological response, and thus risk. In addition, organisms could be affected directly by water quality characteristics. In this context the main objective of this thesis was to investigate the bioavailability of selected ecotoxicologically relevant chemicals (cadmium, benzo(a)pyrene, and pyrene) in various European surface waters and to show the importance of certain water chemistry characteristics in interpreting the bioavailability and toxicity results. The bioavailability of cadmium to Daphnia magna was examined in very soft humic lake water. Humic substances as natural ligands decreased the free and bioavailable proportion of cadmium in soft lake water. As a consequence the uptake rate and the acute toxicity decreased compared with the humic-free reference. When the hardness of humic lake water was artificially elevated, the acute toxicity of cadmium decreased, although the proportion of free cadmium increased. The decreased bioavailability of cadmium in hard water was a result of effective competition for uptake by the hardness cations, especially calcium ions. The protective role of humic substances and water hardness against cadmium toxicity was also observed in Lumbriculus variegatus, although D. magna was more sensitive to cadmium. The bioavailability of two polycyclic aromatic hydrocarbons (PAHs), pyrene and benzo(a)pyrene, was studied in European surface waters of varying water chemistry. Humic substances acted as complexing ligands with both PAHs, but the bioavailability of the more lipophilic benzo(a)pyrene to D. magna was affected more by humic substances than that of pyrene. In addition, not only the quantity of humic substances, but also their quality affected the bioavailability of benzo(a)pyrene. Nevertheless, the humic substances played a protective role in the photo-enhanced toxicity of pyrene under UV-B radiation. Water hardness had no effect on pyrene toxicity. Results indicate that the typical physicochemical characteristics of boreal freshwaters should be considered carefully in local and regional risk assessment of chemicals concerning the Fennoscandian region.

Water Dispersible, Positively and Negatively Charged MoS2 Nanosheets: Surface Chemistry and the Role of Surfactant Binding

Stable aqueous dispersions of atomically thin layered MoS2 nanosheets have been obtained by sonication in the presence of ionic surfactants. The dispersions are stabilized by electrostatic repulsion between the sheets, and we show that the sign of the charge on the MoS2 nanosheets, either positive or negative, can be can be controlled by the choice of the surfactant. Using techniques from solution NMR, we show that the surfactant chains are weakly bound to the MoS2 sheets and undergo rapid exchange with free surfactant chains present in the dispersion. In situ nuclear Overhauser effect spectroscopic measurements provide direct evidence that the surfactant chains lie flat, arranged randomly on the basal plane of the MoS2 nanosheets with their charged headgroup exposed. These results provide a chemical perspective for understanding the stability of these inorganic nanosheets in aqueous dispersions and the origin of the charge on the sheets.