Establishing fluxes of carbon dioxide and a transect of pCO2 during the late fall of precipitation driven Northern fjord

Senior thesis written for Oceanography 445

The Inefficiency of Self-Sufficiency: Uzbekistan's Response to CASA-1000

Thesis (Master's)--University of Washington, 2016-06

Rare earth element geochemistry of Late Devonian reefal carbonates, canning basin, Western Australia: Confirmation of a seawater REE proxy in ancient limestones

Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements (n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average Nd-SN/Yb-SN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement (n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (Nd-SN/Yb-SN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of Devonian seawater REE concentrations from out data are unknown, hypothetical Devonian Canning Basin seawater REE patterns were obtained with coefficients derived from modern natural proxies and experimental values. Resulting Devonian seawater patterns are slightly enriched in LREE compared to most modem seawaters and suggest higher overall REE concentrations, but are very similar to seawaters from regions with high terrigenous inputs. Our results suggest that most limestones should record important aspects of the REE geochemistry of the waters in which they precipitated, provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high, non-seawater-like REE contents. Hence, we expect that many other ancient limestones will serve as seawater REE proxies, and thereby provide information on paleoceanography, paleogeography and geochemical evolution of the oceans. Copyright (C) 2004 Elsevier Ltd.

Application of a novel phytotoxicity assay for the detection of herbicides in Hervey Bay and the Great Sandy Straits

A novel phytotoxicity assay was incorporated into an environmental assessment of Hervey Bay and the Great Sandy Straits, to investigate the role of run-off associated herbicides in the deteriorated health of intertidal seagrass meadows. Dose response curves of common herbicides were performed and their toxicity equivalents elucidated to assist in analysis. The results of the assay were reproducible and corresponded strongly with results of chemical analyses. The incorporation of the assay into the assessment of surface waters added an important aspect to the study by allowing investigation of the toxicity of cumulative herbicide concentrations and yielding biologically relevant data. The highest herbicide concentration detected during the study was equivalent to 0.23 mu g 1(-1) diuron; a concentration known to inhibit photosynthetic efficiency of the assay biomaterial by approximately 3%. (c) 2004 Elsevier Ltd. All rights reserved.

Composition of zooplankton assemblages along the Zagyva River

The species composition, longitudinal distribution and seasonal dynamics of zooplankton were studied in the Zagyva River, Hungary. A total of 108 taxa was recorded from which 61 were new for the river. Rotatoria was the most abundant group, microcrustaceans were less important, only nauplii and copepodites were represented in similar individual numbers. Frequent species included Anuraeopsis fissa, Pompholyx spp., Keratella cochlearis, Brachionus angularis, Bdelloida sp., Bosmina longirostris. Dominance of cosmopolitan species was observed both in the river and its reservoir, and species characteristic of eutrophic waters were of major importance in the latter. There was a downstream decrease in zooplankton densities, which was explained by modified conditions. The relatively large number of individuals in autumn months, and the characteristic large number of individuals in the upper section contrasted general findings of potamoplankton dynamics. On the basis of the species abundance matrix, three river sections can be distinguished (upper, middle, lower section). Due to waste water discharges - received from the Tarján Stream - we found extremely high number of individuals and the lowest diversity at the sampling site Nagybátony (148 rkm).

Identification and localization of polyketide synthase genes from cultures of diarrheic shellfish poisoning toxin producing dinoflagellates of the genus Prorocentrum

Aquatic toxins are responsible for a number of acute and chronic diseases in humans. Okadaic acid (OA) and other dinoflagellate derived polyketide toxins pose serious health risks on a global scale. Ingestion of OA contaminated shellfish causes diarrheic shellfish poisoning (DSP). Some evidence also suggests tumor promotion in the liver by OA. Microcystin-LR (MC-LR) is produced by cyanobacteria and is believed to be the most common freshwater toxin in the US. Humans may be exposed to this acute hepatotoxin through drinking or recreational use of contaminated waters. ^ OA producing dinoflagellates have not been cultured axenically. The presence of associated bacteria raises questions about the ultimate source of OA. Identification of the toxin-producing organism(s) is the first step in identifying the biosynthetic pathways involved in toxin production. Polyketide synthase (PKS) genes of toxic and non-toxic species were surveyed by construction of clonal libraries from PCR amplicons of various toxic and non-toxic species of Prorocentrum in an effort to identify genes, which may be part of the biosynthetic pathway of OA. Analysis of the PKS sequences revealed that toxic species shared identical PKS genes not present in non-toxic species. Interestingly, the same PKS genes were identified in a library constructed from associated bacteria. ^ Subsequent bacterial small subunit RNA (16S) clonal libraries identified several common bacterial species. The most frequent 16S sequences found were identified as species of the genus Roseobacter which has previously been implicated in the production of OA. Attempts to culture commonly occurring bacteria resulted in the isolation of Oceanicaulis alexandrii , a novel marine bacterium previously isolated from the dinoflagellate Alexandrium tamarense, from both P. lima, and P. hoffmanianum. ^ Metabolic studies of microcystin-LR, were conducted to probe the activity of the major human liver cytochromes (CYP) towards the toxin. CYPs may provide alternate routes of detoxification of toxins when the usual routes have been inhibited. For example, some research indicates that cyanobacterial xenobiotics, in particular, lipopolysaccharides may inhibit glutathione S-transferases allowing the toxin to persist long enough to be acted upon by other enzymes. These studies found that at least one human liver CYP was capable of metabolizing the toxin. ^

Changes in Caribbean paleoproductivity, diversity and benthic foraminiferal test size caused by the Neogene closing of the tropical Atlantic-Pacific ocean gateway

The purpose of this study was to test 3 hypotheses: (a) that late Miocene to early Pliocene constriction and complete closure of the Central American Seaway (CAS), connecting tropical Atlantic and East Equatorial Pacific (EEP) oceans, caused decreased productivity in the Caribbean, due to reduced coastal upwelling and an end to the connection with high-productivity Pacific waters, (b) reduced paleoproductivity resulted in decreased diversity in the Caribbean and, (c) this decreased availability of food (reduced paleoproductivity) was responsible for larger mean test size in the three most common benthic foraminiferal species Epistominella exigua, Oridorsalis umbonatus and Globocassidulina subglobosa. ^ These are tested by applying correlation analysis to 7 groups of paleoceanographic proxies, 3 indices of diversity measures and mean test size data from the Caribbean Ocean Drilling Project Site 999, to 47 core samples for the interval between 8.3-2.5 Ma. Results are compared with published Caribbean and Pacific deep-sea records. ^ The Caribbean, between 8.3-7.9 Ma, experienced reduced current velocity and lower ventilation of bottom waters. Thereafter, until 4.2 Ma, the seasonality of phytodetritus input increased and ventilation further reduced. From 4.2-2.5 Ma, paleoproductivity decreased, current velocity reduced, ventilation improved, and the seasonality of phytodetrital input decreased dramatically. The benthic foraminiferal diversity followed the same trend as paleoproductivity. Individual correlation analysis between mean test size of benthic foraminiferal species Epistominella exigua, Oridorsalis umbonatus and Globocassidulina subglobosa and paleoceanographic proxies yielded a positive and significant relationship with paleoproductivity. However, a combined datasets of all 3 species yielded a negative and significant relationship with species abundance. ^ Thus, the study concludes that (a) the gradual closure of the CAS led Caribbean diversity and paleoproductivity to decrease abruptly at 7.9 Ma, when the nutrient-rich Pacific deep waters were cut off, and then, again with the complete closure of the seaway at 4.2 Ma, (b) diversity and paleoproductivity are positively correlated in the Caribbean and (c) that the availability of food is an overriding factor that influences mean test size; lower availability of food and decreased abundance leads to larger test size. ^

Regional climate gradients in precipitation and temperature in response to climate teleconnections in the Greater Everglades ecosystem of South Florida

Precipitation and temperature in Florida responds to climate teleconnections from both the Pacific and Atlantic regions. In this region south of Lake Okeechobee, encompassing NWS Climate Divisions 5, 6, and 7, modern movement of surface waters are managed by the South Florida Water Management District and the US Army Corps of Engineers for flood control, water supply, and Everglades restoration within the constraints of the climatic variability of precipitation and evaporation. Despite relatively narrow, low-relief, but multi-purposed land separating the Atlantic Ocean from the Gulf of Mexico, South Florida has patterns of precipitation and temperature that vary substantially on spatial scales of 101–102 km. Here we explore statistically significant linkages to precipitation and temperature that vary seasonally and over small spatial scales with El Niño-Southern Oscillation (ENSO), the Atlantic Multidecadal Oscillation (AMO), and the Pacific Decadal Oscillation (PDO). Over the period from 1952 to 2005, ENSO teleconnections exhibited the strongest influence on seasonal precipitation. The Multivariate ENSO Index was positively correlated with winter (dry season) precipitation and explained up to 34 % of dry season precipitation variability along the southwest Florida coast. The AMO was the most influential of these teleconnections during the summer (wet season), with significant positive correlations to South Florida precipitation. These relationships with modern climate parameters have implications for paleoclimatological and paleoecological reconstructions, and future climate predictions from the Greater Everglades system.

Origin of salinity variations in Florida Bay

This note presents a method of distinguishing the source of freshwater that causes reductions in salinity in the coastal environment of South Florida. This technique, which uses the 18O and D of the water, allows for differentiation of the freshwater derived from precipitation as opposed to runoff, because surface waters in the Everglades have been highly evaporated and therefore have elevated 18O and dD values relative to precipitation. A time series of monthly 18O and D values of surface waters, collected from stations in Florida Bay between 1993 and 1999, has shown that, during this time, the major source of freshwaters causing depressions in the salinity in the western portion of Florida Bay was derived from precipitation rather than from the runoff of water from the Everglades. In the eastern portion of Florida Bay, close to the boundary between peninsular Florida and the Bay, the proportion of freshwater derived from precipitation drops steadily, reaching <10%. This method not only allows differentiation between the sources of freshwater but can, in a temporal sense, ascertain the effectiveness of water management practices on the salinity of the estuarine ecosystems of South Florida.

Photo degradation of contaminants of emerging concern (CECs) under simulated solar radiation: Implications for their environmental fate

Contaminants of emerging concern (CECs) are continuously being released into the environment mainly because of their incomplete removal in the sewage treatment plants (STPs). The CECs selected for the study include antibiotics (macrolides, sulfonamides and ciprofloxacin), sucralose (an artificial sweetener) and dioctyl sulfosuccinate (DOSS, chemical dispersant used in the Deepwater Horizon oil spill). After being discharged into waterways from STPs, photo degradation is a key factor in dictating the environmental fate of antibiotics and sucralose. Photodegradation efficiency depends on many factors such as pH of the matrix, matrix composition, light source and structure of the molecule. These factors exert either synergistic or antagonistic effects in the environment and thus experiments with isolated factors may not yield the same results as the natural environmental processes. Hence in the current study photodegradation of 13 CECs (antibiotics, sucralose and dicotyl sulfosuccinate) were evaluated using natural water matrices with varying composition (deionized water, fresh water and salt water) as well as radiation of different wavelengths (254 nm, 350 nm and simulated solar radiation) in order to mimic natural processes. As expected the contribution of each factor on the overall rate of photodegradation is contaminant specific, for example under similar conditions, the rate in natural waters compared to pure water was enhanced for antibiotics (2-11 fold), significantly reduced for sucralose (no degradation seen in natural waters) and similar in both media for DOSS. In general, it was observed that the studied compounds degraded faster at 254 nm, while when using a simulated sunlight radiation the rate of photolysis of DOSS increased and the rates for antibiotics decreased in comparison to the 350 nm radiation. The photo stability of the studied CECs followed the order sucralose > DOSS > macrolides > sulfonamides > ciprofloxacin and a positive relationship was observed between photo stability and their ubiquitous presence in natural aquatic matrices. An online LC-MS/MS method was developed and validated for sucralose and further applied to reclaimed waters (n =56) and drinking waters (n = 43) from South Florida. Sucralose was detected in reclaimed waters with concentrations reaching up to 18 μg/L. High frequency of detection (> 80%) in drinking waters indicate contamination of ground waters in South Florida by anthropogenic activity.^