Adição de policloreto de alumínio e remoção de peixes bentívoros como técnicas de restauração de lagos rasos do semiárido brasileiro

Eutrophication is the most common cause of water quality degradation in the world. This process occurs by excessive nutrients inputs, nitrogen and phosphorus, to the aquatic systems resulting in algal and cyanobacterial blooms. In shallow lakes these effects are pronounced due to the higher interaction of the lake with watershed, air and sediment. There are innumerous restoration techniques of eutrophied lakes with a range of successful results but there is only one case of successful lake restoration in Brazil: Paranoá Lake in Brasília city. The Brazilian semiarid region has many artificial lakes, named açudes, which are mostly eutrophic and shallow lakes. The eutrophication in these lakes is reported and the phytoplankton community is dominated by potentially toxic cyanobacteria species, mainly Cylindrospermopsis raciborskii. The aim of this thesis is to test techniques for water quality management which can be easily applied in Brazilian semiarid lakes. Results from a laboratory experiment suggest that the addition of a phosphorus sorbent clay associated with an aluminium based coagulant is an effective technique in removing soluble reactive phosphorus and reducing C. raciborskii growth rate – cyanobacteria potentially toxic dominant in reservoirs of Brazilian semiarid – but this effect is dependent on the biomass in the application moment. Results from a field experiment in mesocosm in a eutrophied lake showed that the addition of aluminium based coagulant and removal of benthivorous fish is more efficient in removing total phosphorus and chlorophyll-a from water column than the isolated application of one of the techniques. Lastly, laboratory tests showed that aluminium based coagulant exhibited good performance in removing turbidity and total phosphorus from water of six reservoirs but the efficiency was reduced by algal biomass and pH. The results of this study showed that the improvement in water quality of eutrophied reservoirs in semiarid region is possible through internal loading control by phosphorus precipitation and inactivation in sediments or inhibition of phosphorus release by benthivorous fishes, and also that these results show are additives in water quality improvement.

Effects of introduced moose (Alces alces) on vegetation composition, nutrient dynamics, and decomposition rates in boreal forest ecosystems in Newfoundland, Canada

Globally, consumers affect ecosystem processes including nutrient dynamics. Herbivores have been known to slow nutrient flow in boreal forest ecosystems. I examined the effects of introduced moose on disturbed forests of Newfoundland, Canada by conducting a field experiment during August - November 2014 in 20 paired moose exclosure-control plots. I tested whether moose browsing directly and indirectly affected forests by measuring plant species composition, litter quality and quantity, soil quality, and decomposition rates in areas moose exclosure-control plots. I analyzed moose effects using linear mixed effects models and found evidence indicating that moose reduce plant height and litter biomass affecting the availability of carbon, nitrogen, and phosphorus. However, plant diversity, soil quality, and litter decomposition did not differ between moose exclosures and controls. Moose in Newfoundland directly influence plant regeneration and litter biomass while indirect effects on soil ecosystems may be limited by time, disturbance, and climate.

Pore water and solid-phase measurements on sediment cores from the Black Sea

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe) oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ. Here we combine detailed geochemical analyses of the sediment and pore water with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P) and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. Our results show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g. vivianite) are converted to sulfide phases, leading to an enrichment in solid phase S and the release of phosphate to the pore water. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front. Our model results further demonstrate that downward migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM (~ 1-100 pmol/cm**3/d) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the pore water at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.

Identifying the Structure and Fate of Wastewater Derived Organic Micropollutants by High-resolution Mass Spectrometry

Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.

The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment.

In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.

I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters.

Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.

Viral, bacterial and ciliate abundance and viral-bacterial diversity in mesocosm experiments, 2007-2008, Kongsfjorden

Two mesocosm experiments, PAME-I and PAME-II were conducted in 2007 and 2008 to investigate fate of organic carbon in the arctic microbial food web. Mesocosms were nutrient fertilized initially to induce phytoplankton bloom development. In PAME-I eight units (each 700 L) formed two four point gradients of additional DOC in form of glucose (0, 0.5, 1 and 3 times Redfield ratio in terms of carbon relative to the nitrogen and phosphorus additions) (Fig. 1). All the eight units also got a daily dose of NH4+ and PO4**3- in Redfield ratio. Two gradients were set up, one with silicate addition, performed in the Arctic location Ny Ålesund, Svalbard, have previously been reported to give different food-web level responses to similar nutrient perturbations. In PAME-II all ten units (each 900 L) formed two four point gradients of additional DOC in form of glucose (0, 0.5, 1, 2 and 3 times Redfield ratio in terms of carbon relative to nitrogen and phosphorus additions). The two gradients in glucose were kept silicate replete. NH4+ was used as the DIN source in one gradient (units 1 to 5) and NO3- in the other (units 6-9). All units got a daily dose of PO4**3- in Redfield ratio. Prokaryotes and viruses were measured by flow cytometry, while ciliate abundances were counted using a Flow Cam. Viral and bacterial diversity was measured by PFGE and DGGE, respectively. In PAME-II the abundance of ciliates was lower than in PAME-I, presumably caused by higher copepod grazing. The abundances of prokaryotes and viruses were also lower in PAME-II compared to PAME-I. Further, less diversity was detected in the viral community (FCM and PFGE) in PAME-II, and no response was observed in the bacterial community structure due to addition of organic carbon.

Comparison of nitrogen isotopic values from different preparation methods

We are writing to comment on the work of Tamburini et al. (2003, doi:10.1029/2000PA000616). During the course of subsequent discussions between the authors and ourselves, it has become clear that the published sedimentary nitrogen isotopic values for Ocean Drilling Program (ODP) Site 724 are in error. Our reanalysis of sediment samples from the same intervals has revealed a significant offset from the original d15N data, requiring a revised assessment of their initial interpretation. The purposes of this comment are to (1) address the origin of these errors; (2) outline a protocol for future validation of nitrogen isotopic analyses; and (3) provide revised interpretations of the sedimentary d15N data in terms of the regional relative contributions of denitrification and nitrogen fixation and mean state of the southwest monsoon. (2) Nitrogen isotopic values measured on late Quaternary sediments at Arabian Sea ODP Site 724 by Tamburini et al. (2003, doi:10.1029/2000PA000616) are inexplicably different from a number of published records of d15N from very nearby on the Oman margin (Altabet et al., 1995, doi:10.1038/373506a0; 1999, doi:10.1029/1999PA900035; 2002, doi:10.1038/415159a; Higginson et al., 2004, doi:10.1016/j.gca.2004.03.015) and elsewhere in the Arabian Sea (Reichart et al., 1998, doi:10.1029/98PA02203). These data were generated using similar instrumentation (elemental analyzer coupled with an isotope ratio mass spectrometer) and analytical methodology to those already published. Concerned by this clear discrepancy, we analyzed aliquots of sediment from the same depth intervals for nitrogen abundance and bulk sedimentary nitrogen isotopes. We have been unable to duplicate the values published by Tamburini et al. (2003, doi:10.1029/2000PA000616 ), even after analysis of multiple replicates and due consideration of natural sediment heterogeneities and postrecovery sample storage.

Geomicrobiology, bulk sediment characteristics and pore water chemistry of sediment cores from Laguna Potrok Aike, southern Patagonia

Authigenic minerals can form in the water column and sediments of lakes, either abiotically or mediated by biological activity. Such minerals have been used as paleosalinity and paleoproductivity indicators and reflect trophic state and early diagenetic conditions. They are also considered potential indicators of past and perhaps ongoing microbial activity within sediments. Authigenic concretions, including vivianite, were described in late glacial sediments of Laguna Potrok Aike, a maar lake in southernmost Argentina. Occurrence of iron phosphate implies specific phosphorus sorption behavior and a reducing environment, with methane present. Because organic matter content in these sediments was generally low during glacial times, there must have been alternative sources of phosphorus and biogenic methane. Identifying these sources can help define past trophic state of the lake and diagenetic processes in the sediments. We used scanning electron microscopy, phosphorus speciation in bulk sediment, pore water analyses, in situ ATP measurements, microbial cell counts, and measurements of methane content and its carbon isotope composition (d13C CH4) to identify components of and processes in the sediment. The multiple approaches indicated that volcanic materials in the catchment are important suppliers of iron, sulfur and phosphorus. These elements influence primary productivity and play a role in microbial metabolism during early diagenesis. Authigenic processes led to the formation of pyrite framboids and revealed sulfate reduction. Anaerobic oxidation of methane and shifts in pore water ion concentration indicated microbial influence with depth. This study documents the presence of active microbes within the sediments and their relationship to changing environmental conditions. It also illustrates the substantial role played by microbes in the formation of Laguna Potrok Aike concretions. Thus, authigenic minerals can be used as biosignatures in these late Pleistocene maar sediments.

Radium 228 and Radium 226 in surface water of the Kara Sea and Laptev Sea

The surface water in the Transpolar Drift in the Arctic Ocean has a strong signature of 228Ra. In an earlier study of 228Ra in the open Arctic we showed that the major 228Ra source had to be in the Siberian shelf seas, but only a single shelf station was published so far. Here we investigate the sources of this signal on the Siberian shelves by measurements of 228Ra and 226Ra in surface waters of the Kara and Laptev Sea, including the Ob, Yenisey and Lena estuaries. In the Ob and Lena rivers we found an indication for a very strong and unexpected removal of both isotopes in the early stage of estuarine mixing, presumably related to flocculation of organic-rich material. Whereas 226Ra behaves conservatively on the shelf, the distribution of 228Ra is governed by large inputs on the shelves, although sources are highly variable. In the Kara Sea the maximum activity was found in the Baydaratskaya Bay, where tidal resonance and low freshwater supply favour 228Ra accumulation. The Laptev Sea is a stronger source for 228Ra than the Kara Sea. Since a large part of Kara Sea water flows through the Laptev Sea, the 228Ra signal in the Transpolar Drift can be described as originating on the Laptev shelf. The combined freshwater inputs from the Eurasian shelves thus produce a common radium signature with a 228Ra/226Ra activity ratio of 4.0 at 20% river water. The radium signals of the individual Siberian rivers and shelves cannot be separated, but their signal is significantly different from the signal produced on the Canadian shelf (Smith et al., in press). In this respect, the radium tracers add to the information given by Barium. Moreover, with the 5.8 year half-life of 228Ra, they have the potential to serve as a tracer for the age of a water mass since its contact with the shelves.

Seawater carbonate chemistry, nutrient uptake and biological processes of coral Stylophora pistillata during experiments, 2011

The effects of ocean acidification and elevated seawater temperature on coral calcification and photosynthesis have been extensively investigated over the last two decades, whereas they are still unknown on nutrient uptake, despite their importance for coral energetics. We therefore studied the separate and combined impacts of increases in temperature and pCO2 on phosphate, ammonium, and nitrate uptake rates by the scleractinian coral S. pistillata. Three experiments were performed, during 10 days i) at three pHT conditions (8.1, 7.8, and 7.5) and normal temperature (26°C), ii) at three temperature conditions (26°, 29°C, and 33°C) and normal pHT(8.1), and iii) at three pHT conditions (8.1, 7.8, and 7.5) and elevated temperature (33°C). After 10 days of incubation, corals had not bleached, as protein, chlorophyll, and zooxanthellae contents were the same in all treatments. However, photosynthetic rates significantly decreased at 33°C, and were further reduced for the pHT 7.5. The photosynthetic efficiency of PSII was only decreased by elevated temperature. Nutrient uptake rates were not affected by a change in pH alone. Conversely, elevated temperature (33°C) alone induced an increase in phosphate uptake but a severe decrease in nitrate and ammonium uptake rates, even leading to a release of nitrogen into seawater. Combination of high temperature (33°C) and low pHT(7.5) resulted in a significant decrease in phosphate and nitrate uptake rates compared to control corals (26°C, pHT = 8.1). These results indicate that both inorganic nitrogen and phosphorus metabolism may be negatively affected by the cumulative effects of ocean warming and acidification.

Seawater carbonate chemistry, structural and chemical characteristics of the seagrass Thalassia testudinum in an situ CO2 enrichment experiment

Seagrasses commonly display carbon-limited photosynthetic rates. Thus, increases in atmospheric pCO2, and consequentially oceanic CO2(aq) concentrations, may prove beneficial. While addressed in mesocosms, these hypotheses have not been tested in the field with manipulative experimentation. This study examines the effects of in situ CO2(aq) enrichment on the structural and chemical characteristics of the tropical seagrass, Thalassia testudinum. CO2(aq) availability was manipulated for 6 months in clear, open-top chambers within a shallow seagrass meadow in the Florida Keys (USA), reproducing forecasts for the year 2100. Structural characteristics (leaf area, leaf growth, shoot mass, and shoot density) were unresponsive to CO2(aq) enrichment. However, leaf nitrogen and phosphorus content declined on average by 11 and 21 %, respectively. Belowground, non-structural carbohydrates increased by 29 %. These results indicate that increased CO2(aq) availability may primarily alter the chemical composition of seagrasses, influencing both the nutrient status and resilience of these systems.

Seawater carbonate chemistry, nutrients, and Calcidiscus leptoporus (strain RCC1135) growth rate and calcification rate during experiments, 2012

The coccolithophore Calcidiscus leptoporus was grown in batch culture under nitrogen (N) as well as phosphorus (P) limitation. Growth rate, particulate inorganic carbon (PIC), particulate organic carbon (POC), particulate organic nitrogen (PON), and particulate organic phosphorus (POP) production were determined and coccolith morphology was analysed. While PON production decreased by 70% under N-limitation and POP production decreased by 65% under P-limitation, growth rate decreased by 33% under N- as well as P-limitation. POC as well as PIC production (calcification rate) increased by 27% relative to the control under P-limitation, and did not change under N-limitation. Coccolith morphology did not change in response to either P or N limitation. While these findings, supported by a literature survey, suggest that coccolith morphogenesis is not hampered by either P or N limitation, calcification rate might be. The latter conclusion is in apparent contradiction to our data. We discuss the reasons for this inference.

Nitrite consumption and associated isotope changes during a river flood event in the Elbe river

In oceans, estuaries, and rivers, nitrification is an important nitrate source, and stable isotopes of nitrate are often used to investigate recycling processes (e.g. remineralisation, nitrification) in the water column. Nitrification is a two-step process, where ammonia is oxidised via nitrite to nitrate. Nitrite usually does not accumulate in natural environments, which makes it difficult to study the single isotope effect of ammonia oxidation or nitrite oxidation in natural systems. However, during an exceptional flood in the Elbe River in June 2013, we found a unique co-occurrence of ammonium, nitrite, and nitrate in the water column, returning towards normal summer conditions within 1 week. Over the course of the flood, we analysed the evolution of d15N-[NH4]+ and d15N-[NO2]- in the Elbe River. In concert with changes in suspended particulate matter (SPM) and d15N SPM, as well as nitrate concentration, d15N-NO3 - and d18O-[NO3] -, we calculated apparent isotope effects during net nitrite and nitrate consumption. During the flood event, > 97 % of total reactive nitrogen was nitrate, which was leached from the catchment area and appeared to be subject to assimilation. Ammonium and nitrite concentrations increased to 3.4 and 4.4 µmol/l, respectively, likely due to remineralisation, nitrification, and denitrification in the water column. d15N-[NH4]+ values increased up to 12 per mil, and d15N-[NO2]- ranged from -8.0 to -14.2 per mil. Based on this, we calculated an apparent isotope effect 15-epsilon of -10.0 ± 0.1 per mil during net nitrite consumption, as well as an isotope effect 15-epsilon of -4.0 ± 0.1 per mil and 18-epsilon of -5.3 ± 0.1 per mil during net nitrate consumption. On the basis of the observed nitrite isotope changes, we evaluated different nitrite uptake processes in a simple box model. We found that a regime of combined riparian denitrification and 22 to 36 % nitrification fits best with measured data for the nitrite concentration decrease and isotope increase.

Soil properties and microbial indicators of samples from Lake Wellman, Darwin Mountains, Antarctica

Four pedons on each of four drift sheets in the Lake Wellman area of the Darwin Mountains were sampled for chemical and microbial analyses. The four drifts, Hatherton, Britannia, Danum, and Isca, ranged from early Holocene (10 ka) to mid-Quaternary (c. 900 ka). The soil properties of weathering stage, salt stage, and depths of staining, visible salts, ghosts, and coherence increase with drift age. The landforms contain primarily high-centred polygons with windblown snow in the troughs. The soils are dominantly complexes of Typic Haplorthels and Typic Haploturbels. The soils were dry and alkaline with low levels of organic carbon, nitrogen and phosphorus. Electrical conductivity was high accompanied by high levels of water soluble anions and cations (especially calcium and sulphate in older soils). Soil microbial biomass, measured as phospholipid fatty acids, and numbers of culturable heterotrophic microbes, were low, with highest levels detected in less developed soils from the Hatherton drift. The microbial community structure of the Hatherton soil also differed from that of the Britannia, Danum and Isca soils. Ordination revealed the soil microbial community structure was influenced by soil development and organic carbon.

(Table 1) Bulk Fe isotope values and pyrite framboids sizes of Cenomanian-Turonian samples

Organic carbon-rich shales from localities in England, Italy, and Morocco, which formed during the Cenomanian-Turonian oceanic anoxic event (OAE), have been examined for their total organic carbon (TOC) values together with their carbon, nitrogen, and iron isotope ratios. Carbon isotope stratigraphy (d13Corg and d13Ccarb) allows accurate recognition of the strata that record the oceanic anoxic event, in some cases allowing characterization of isotopic species before, during, and after the OAE. Within the black shales formed during the OAE, relatively heavy nitrogen isotope ratios, which correlate positively with TOC, suggest nitrate reduction (leading ultimately to denitrification and/or anaerobic ammonium oxidation). Black shales deposited before the onset of the OAE in Italy have unusually low bulk d57Fe values, unlike those found in the black shale (Livello Bonarelli) deposited during the oceanic anoxic event itself: These latter conform to the Phanerozoic norm for organic-rich sediments. Pyrite formation in the pre-OAE black shales has apparently taken place via dissimilatory iron reduction (DIR), within the sediment, a suboxic process that causes an approximately -2 per mil fractionation between a lithogenic Fe(III)oxide source and Fe(II)aq. In contrast, bacterial sulfate reduction (BSR), at least partly in the water column, characterized the OAE itself and was accompanied by only minor iron isotope fractionation. This change in the manner of pyrite formation is reflected in a decrease in the average pyrite framboid diameter from ~10 to ~7 µm. The gradual, albeit irregular increase in Fe isotope values during the OAE, as recorded in the Italian section, is taken to demonstrate limited isotopic evolution of the dissolved iron pool, consequent upon ongoing water column precipitation of pyrite under euxinic conditions. Given that evidence exists for both nitrate and sulfate reduction during the OAE, it is evident that redox conditions in the water column were highly variable, in both time and space.