Composition of a protein-like fluorophore of dissolved organic matter in coastal wetland and estuarine ecosystems

This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation–emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r2=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5×104 (T1) and ∼7.6×103 (T2) and with varying relative abundance among samples. The T1-peak intensity correlated strongly with [UDON] (r2=0.516, p<0.001), while T2-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.

Cytotoxicity in L929 fibroblasts and inhibition of herpes simplex virus type 1 Kupka by estuarine cyanobacteria extracts

The cyanobacteria are known to be a rich source of metabolites with a variety of biological activities in different biological systems. In the present work, the bioactivity of aqueous and organic (methanolic and hexane) crude extracts of cyanobacteria isolated from estuarine ecosystems was studied using different bioassays. The assessment of DNA damage on the SOS gene repair region of mutant PQ37 strain of Escherichia coli was performed. Antiviral activity was evaluated against influenza virus, HRV-2, CVB3 and HSV-1 viruses using crystal violet dye uptake on HeLa, MDCK and GMK cell lines. Cytotoxicity evaluation was performed with L929 fibroblasts by MTT assay. Of a total of 18 cyanobacterial isolates studied, only the crude methanolic extract of LEGE 06078 proved to be genotoxic (IF > 1.5) in a dose-dependent manner and other four were putative candidates to induce DNA damage. Furthermore, the crude aqueous extract of LEGE 07085 showed anti- herpes type 1 activity (IC50 = 174.10 μg dry extract mL−1) while not presenting any cytotoxic activity against GMK cell lines. Of the 54 cyanobacterial extracts tested, only the crude methanolic and hexane ones showed impair on metabolic activity of L929 fibroblasts after long exposure (48–72 h). The inhibition of HSV-1 and the strong cytotoxicity against L929 cells observed emphasizes the importance of evaluating the impact of those estuarine cyanobacteria on aquatic ecosystem and on human health. The data also point out their potential application in HSV-1 treatment and pharmacological interest.

Triterpenoids as Biomarkers of Mangrove Organic Matter in Cochin Estuarine System

This thesis entitled triterpenoids as biomarkers of mangrove organic matter in cochin estuarine system.Mangrove forests, known as rainforests of the sea are one of the most important coastal ecosystems in the world in terms of primary production and coastal protection.Estuaries, the important areas of world’s coastal zones link the carbon cycle of the oceans to the continents.Three mangrove ecosystems and three estuarine stations around Cochin region, southwest coast of India were selected for the present study. The thesis is divided into five chapters. Chapter 1 is the Introduction and it deals with the aim and scope of the present study. Chapter 2 is Materials and Methods. This chapter deals with the nature and general geographical features of the study area. It also contains the details of the sampling and analytical methodology.the present study. Chapter 3 is Geochemistry and it includes the seasonal and spatial variations of the geochemical parameters in the surface sediments.Chapter 4 is Biochemical Composition. It covers the biochemical composition of organic matter in the surface sediments to examine the quality and quantity of organic matter.Chapter 5, Triterpenoid Biomarkers in Sediments, characterize the organic matter in the sediments of the mangrove and estuarine ecosystems under study, to assess the possible sources with the help of triterpenoid biomarkers along with other lipid biomarkers.

Fate and effects of drilling wastes in a shallow estuarine mesocosm

To address concerns expressed about the possible effect of drilling mud discharges on shallow, low-energy estuarine ecosystems, a 12 month study was designed to detect alterations in water quality and sediment geochemistry. Each drilling mud used in the study and sediments from the study site were analyzed in the laboratory for chemical and physical characteristics. Potential water quality impacts were simulated by the EPA-COE elutriation test procedure. Mud toxicity was measured by acute and chronic bioassays with Mysidopsis bahia, Mercenaria mercenaria, and Nereis virens.^ For the field study, a relatively pristine, shallow (1.2 m) estuary (Christmas Bay, TX) without any drilling activity for the last 30 years was chosen for the study site. After a three month baseline study, three stations were selected. Station 1 was an external control. At each treatment station (2, 3), mesocosms were constructed to enclose a 3.5 m$\sp3$ water column. Each treatment station included an internal control site also. Each in situ mesocosm, except the controls, was successively dosed at a mesocosm-specific dose (1:100; 1:1,000; or 1:10,000 v/v) with 4 field collected drilling muds (spud, nondispersed, lightly-treated, and heavily-treated lignosulfonate) in sequential order over 1.5 months. Twenty-four hours after each dose, water exchange was allowed until the next treatment. Station 3 was destroyed by a winter storm. After the last treatment, the enclosures were removed and the remaining sites monitored for 6 months. One additional site was similarly dosed (1:100 v/v) with clean dredged sediment from Christmas Bay for comparison between dredged sediments and drilling muds.^ Results of the analysis of the water samples and field measurements showed that water quality was impacted during the discharges, primarily at the highest dose (1:100 v/v), but that elevated levels of C, Cr (T,F), Cr$\sp{+3}$ (T, F), N, Pb, and Zn returned to ambient levels before the end of the 24 hour exposure period or immediately after water exchange was allowed (Al, Ba(T), Chlorophyll ABC, SS, %T). Barium, from the barite, was used as a geochemical tracer in the sediments to confirm estimated doses by mass balance calculations. Barium reached a maximum of 166x background levels at the high dose mesocosm. Barium levels returned to ambient or only slightly elevated levels at the end of the 6 month monitoring period due to sediment deposition, resuspension, and bioturbation. QA/QC results using blind samples consisting of lab standards and spiked samples for both water and sediment matrices were within acceptable coefficients of variation.^ In order to avoid impacts on water quality and sediment geochemistry in a shallow estuarine ecosystem, this study concluded that a minimal dilution of 1:1,000 (v/v) would be required in addition to existing regulatory constraints. ^

Mangrove tannins in aquatic ecosystems: Their fate and possible influence on dissolved organic carbon and nitrogen cycling

We describe the fate of mangrove leaf tannins in aquatic ecosystems and their possible influence on dissolved organic nitrogen (DON) cycling. Tannins were extracted and purified from senescent yellow leaves of the red mangrove (Rhizophora mangle) and used for a series of model experiments to investigate their physical and chemical reactivity in natural environments. Physical processes investigated included aggregation, adsorption to organic matter-rich sediments, and co-aggregation with DON in natural waters. Chemical reactions included structural change, which was determined by excitation–emission matrix fluorescence spectra, and the release of proteins from tannin–protein complexes under solar-simulated light exposure. A large portion of tannins can be physically eliminated from aquatic environments by precipitation in saline water and also by binding to sediments. A portion of DON in natural water can coprecipitate with tannins, indicating that mangrove swamps can influence DON cycling in estuarine environments. The chemical reactivity of tannins in natural waters was also very high, with a half-life of less than 1 d. Proteins were released gradually from tannin–protein complexes incubated under light conditions but not under dark conditions, indicating a potentially buffering role of tannin– protein complexes on DON recycling in mangrove estuaries. Although tannins are not detected at a significant level in natural waters, they play an important ecological role by preserving nitrogen and buffering its cycling in estuarine ecosystems through the prevention of rapid DON export/loss from mangrove fringe areas and/or from rapid microbial mineralization.

Eastern oysters (Crassostrea virginica) as an indicator for restoration of Everglades Ecosystems

The Comprehensive Everglades Restoration Plan (CERP) attempts to restore hydrology in the Northern and Southern Estuaries of Florida. Reefs of the Eastern oyster Crassostrea virginica are a dominant feature of the estuaries along the Southwest Florida coast. Oysters are benthic, sessile, filter-feeding organisms that provide ecosystem services by filtering the water column and providing food, shelter and habitat for associated organisms. As such, the species is an excellent sentinel organism for examining the impacts of restoration on estuarine ecosystems. The implementation of CERP attempts to improve: the hydrology and spatial and structural characteristics of oyster reefs, the recruitment and survivorship of C. virginica, and the reef-associated communities of organisms. This project links biological responses and environmental conditions relative to hydrological changes as a means of assessing positive or negative trends in oyster responses and population trends. Using oyster responses, we have developed a communication tool (i.e., Stoplight Report Card) based on CERP performance measures that can distinguish between responses to restoration and natural patterns. The Stoplight Report Card system is a communication tool that uses Monitoring and Assessment Program (MAP) performance measures to grade an estuary's response to changes brought about by anthropogenic input or restoration activities. The Stoplight Report Card consists of both a suitability index score for each organism metric as well as a trend score (− decreasing trend, +/− no change in trend, and + increasing trend). Based on these two measures, a component score (e.g., living density) is calculated by averaging the suitability index score and the trend score. The final index score is obtained by taking the geometric score of each component, which is then translated into a stoplight color for success (green), caution (yellow), or failure (red). Based on the data available for oyster populations and the responses of oysters in the Caloosahatchee Estuary, the system is currently at stage “caution.” This communication tool instantly conveys the status of the indicator and the suitability, while trend curves provide information on progress towards reaching a target. Furthermore, the tool has the advantage of being able to be applied regionally, by species, and collectively, in concert with other species, system-wide.

Environmental data management in the Sado Estuary

Estuaries are perhaps the most threatened environments in the coastal fringe; the coincidence of high natural value and attractiveness for human use has led to conflicts between conservation and development. These conflicts occur in the Sado Estuary since its location is near the industrialised zone of Peninsula of Setúbal and at the same time, a great part of the Estuary is classified as a Natural Reserve due to its high biodiversity. These facts led us to the need of implementing a model of environmental management and quality assessment, based on methodologies that enable the assessment of the Sado Estuary quality and evaluation of the human pressures in the estuary. These methodologies are based on indicators that can better depict the state of the environment and not necessarily all that could be measured or analysed. Sediments have always been considered as an important temporary source of some compounds or a sink for other type of materials or an interface where a great diversity of biogeochemical transformations occur. For all this they are of great importance in the formulation of coastal management system. Many authors have been using sediments to monitor aquatic contamination, showing great advantages when compared to the sampling of the traditional water column. The main objective of this thesis was to develop an estuary environmental management framework applied to Sado Estuary using the DPSIR Model (EMMSado), including data collection, data processing and data analysis. The support infrastructure of EMMSado were a set of spatially contiguous and homogeneous regions of sediment structure (management units). The environmental quality of the estuary was assessed through the sediment quality assessment and integrated in a preliminary stage with the human pressure for development. Besides the earlier explained advantages, studying the quality of the estuary mainly based on the indicators and indexes of the sediment compartment also turns this methodology easier, faster and human and financial resource saving. These are essential factors to an efficient environmental management of coastal areas. Data management, visualization, processing and analysis was obtained through the combined use of indicators and indices, sampling optimization techniques, Geographical Information Systems, remote sensing, statistics for spatial data, Global Positioning Systems and best expert judgments. As a global conclusion, from the nineteen management units delineated and analyzed three showed no ecological risk (18.5 % of the study area). The areas of more concern (5.6 % of the study area) are located in the North Channel and are under strong human pressure mainly due to industrial activities. These areas have also low hydrodynamics and are, thus associated with high levels of deposition. In particular the areas near Lisnave and Eurominas industries can also accumulate the contamination coming from Águas de Moura Channel, since particles coming from that channel can settle down in that area due to residual flow. In these areas the contaminants of concern, from those analyzed, are the heavy metals and metalloids (Cd, Cu, Zn and As exceeded the PEL guidelines) and the pesticides BHC isomers, heptachlor, isodrin, DDT and metabolits, endosulfan and endrin. In the remain management units (76 % of the study area) there is a moderate impact potential of occurrence of adverse ecological effects and in some of these areas no stress agents could be identified. This emphasizes the need for further research, since unmeasured chemicals may be causing or contributing to these adverse effects. Special attention must be taken to the units with moderate impact potential of occurrence of adverse ecological effects, located inside the natural reserve. Non-point source pollution coming from agriculture and aquaculture activities also seem to contribute with important pollution load into the estuary entering from Águas de Moura Channel. This pressure is expressed in a moderate impact potential for ecological risk existent in the areas near the entrance of this Channel. Pressures may also came from Alcácer Channel although they were not quantified in this study. The management framework presented here, including all the methodological tools may be applied and tested in other estuarine ecosystems, which will also allow a comparison between estuarine ecosystems in other parts of the globe.

Sediment quality assessment in a tropical estuary: The case of Ceará River, Northeastern Brazil

The present study aimed to assess the sediment quality in a tropical estuary located in the northeast of Brazil under semi-arid conditions and multiple sources of contamination, using both toxicity bioassays and metal distribution. The metal distribution followed a concentration gradient decreasing one order of magnitude from the inner station toward the outer estuary, with amounts in the following order: Fe > Al > Zn > Cr > Pb > Cu. The index of geoaccumulation indicated a metal enrichment in the Ceará river sediment, mainly at inner sites, considered from moderately to strongly contaminated by Al, Cu, Cr and Zn. Sediment samples were considered toxic by means of whole sediment tests with copepods (reproduction) and amphipods (survival), and also elutriate fraction and sediment-water interface with sea urchin embryos (development). Acute and chronic toxicity did not exhibit a significant correlation with metals, emphasizing the influence of other contaminants mainly related to the pollution sources installed in the mid-estuary. © 2013 Elsevier Ltd. All rights reserved.

Low levels of genetic diversity depicted from mitochondrial DNA sequences in a heavily exploited marine fish (Cynoscion acoupa, Sciaenidae) from the Northern coast of Brazil

The acoupa weakfish (Cynoscion acoupa - Sciaenidae) is a marine species of croaker with estuarine-dependent behavior, found in the western Atlantic from Panama to Argentina. It is one of the most exploited food fish on the northern coast of Brazil. In this study, DNA sequences were determined from the entire control region (D-loop) of the mitochondrial genome of 297 individuals collected during seven different months between December 2003 and August 2005 on the northern coast of Brazil (Amapá and Pará). Genetic variability expressed by haplotype (h = 0,892) and nucleotide (p = 0,003) diversities were low compared to other heavily exploited marine fish species from the western Atlantic and eastern Asia. AMOVA depicted a lack of genetic structuring among the samples from different years, indicating the presence of a single stock of C. acoupa within the sample area. The possible reasons for the low levels of genetic diversity are discussed. These results demonstrate a need for the monitoring of C. acoupa harvesting and the preservation of the estuaries within its geographic range, considering that this large fish depends on estuarine ecosystems during part of its life cycle.

Ecologia da ictiofauna do estuário do rio Paciência, Ilha do Maranhão - Brasil

Os sistemas estuarinos funcionam como importante habitat para várias especies de peixes, atraves das redes de canais de mare. Sob o ponto de vista ecologico, a comunidade ictiofaunística desempenham importante funcao no balanco energetico dos varios niveis tróficos dos ecossistemas estuarinos. Neste contexto, o presente estudo objetivou: determinar as distribuições espaco-temporais da ictiofauna; explicar suas características comportamentais e ecologicas; comparar a composicao da biomassa relativa, guildas ecologicas e funcionais em diferentes sistemas estuarinos da costa Norte; investigar a influencia das variaveis bioticas e abioticas e sua correlacao com os padroes biologicos da ictiofauna e identificar alteracoes na integridade biotica dos canais de mare estudados, utilizando a ictiofauna. Os dados foram obtidos a partir de amostragens bimestrais nos canais de mare Iguaiba, Grande e Cristovao, no periodo de janeiro/2006 a setembro/2007, utilizando redes de emalhar e tapagem. Paralelamente, foram tomadas amostras na camada superficial da agua para determinacao das variaveis fisico-quimicos e dos nutrientes inorganicos dissolvidos. Na caracterizacao ecologica das especies, foram empregados indices que estimam a diversidade, equitabilidade e riqueza. O Indice de Integridade Biotica foi aplicado para avaliar os efeitos das possiveis alteracoes ambientais na ictiofauna. Tecnicas univariadas (ANOVA, Kruskall-Wallis) e multivariadas (Cluster, nMDS, SIMPER, COIA e curvas ABC) foram usadas para comparar as especies e os locais de capturas. No total foram capturados 12.219 peixes distribuídos em 55 especies e 27 familias. As familias Sciaenidae, Ariidae, Carangidae, Engraulidae e Mugilidae apresentaram maior riqueza de especies. Ariopsis bonillai e Cetengraulis edentulus, apresentaram maior contribuicao para a formacao de grupos mais similares; Stellifer naso e Cynoscion acoupa foram responsaveis pela dissimilaridade entre os grupos formados. Cerca de 66% dos peixes capturados foram representados por individuos jovens, confirmando a condicao de bercario dos sistemas estuarinos. Os registros ictiofaunisticos entre o Golfao Marajoara e Maranhense apontam a ocorrência de 140 especies. Especies marinhas visitantes ocasionais e de agua doce ocorreram ocasionalmente. Marinhas estuarino-oportunistas e estuarino dependentes apresentaram maior contribuicao no Golfao Maranhense, ja as estuarino residentes apresentaram biomassa elevada em todos os sistemas estuarinos investigados. Detritivoros ocorreram principalmente no Pará e zoobentivoros no Maranhao. A ocorrencia de piscivoros foi inversamente proporcional a abundancia de juvenis. A co-estrutura formada entre variaveis ambientais-peixes foi significativa. As variaveis salinidade, pH, silicato, amonio, fosfato e nitrato influenciaram na estrutura da ictiofauna. Nenhuma especie se associou a ambientes com elevadas concentracoes de nutrientes inorganicos. As curvas ABC demonstraram que o ambiente estuarino encontra-se moderadamente perturbado, enquanto o indice de integridade caracterizou a qualidade ambiental dos canais de mare entre muito pobre a regular. O estudo mostrou que os canais de mare são importantes areas de criacao devido a dominancia de juvenis; a ictiofauna apresenta sazonalidade em relacao aos periodos hidrologicos; a comunidade peixes presente nos canais de mare pode atuar como indicadora da qualidade de ecossistemas submetidos a pulsos de mares. Considera-se, portanto, a protecao dos canais entre-mares dos manguezais uma ação essencial para o manejo dos recursos pesqueiros, uma vez que existe uma forte relacao entre abundancia da ictiofauna e a composição estrutural do habitat.

Population structure and distribution of UCA ( Brachyura: Ocypodidae) influenced by abiotic factors in a tropical estuary

Uca populations have an important functional and structural role in many estuarine ecosystems. These crabs exhibit distinct physiological tolerance to salinity gradients, which may partially explain their heterogeneous distribution. In order to investigate the population structure and distribution of Uca spp. in a tropical estuary, we sampled Uca crabs in replicated 0.75 m2 quadrats at six muddy plain areas during monthly intervals between July and November 2012 in spring tidal conditions. Environmental factors including water temperature, salinity, sediment total organic matter, chlorophyll-a, and granulometry were analyzed. We sampled a total of 2919 individuals distributed in three Uca species (U. uruguayensis, U. thayeri and U. maracoani), from which U. uruguayensis was dominant. The density and biomass of individuals were spatially and temporally heterogeneous. During October and November we found higher Uca spp. densities (71.3 ± 47.3 to 77.6 ± 44,5 ind. 0.75 m-²) and biomass (1.8 ± 1.1 to 2.1 ± 1.0 g 0.75 m-2 AFDW) if compared to the previous months, density (July 55,5± 44,1 August 52,5± 34,9 and September 47,7 ± 25,6 ind. 0,75m-²) and biomass in others months (July 1,0± 0,94 August 1,1 ± 0,72 and September 1,3±0,93 g 0.75 m-2 AFDW ). The same pattern was found for other variables, such as salinity (32 and 34), organic matter (30 and 67%) and chlorophyll-a (89 and 46 μg g-1). In two study areas we found this pattern which suggests that higher Uca productivity and food availability are related. A principal component analysis (PCA) suggests that salinity and granulometry (silt) can influence (60% correspondence) the distribution of U. maracoani. For U. uruguayensis and U. thayeri the PCA suggests chlorophyll-a was important, which is a good indicator for labile organic matter. Our study suggests that the population structure and distribution of Uca species may be regulated by food availability, supporting their utility as biological models for ecosystem monitoring.

Bioremediation of PAHs - Limitations and soultions

Introduction 1.1 Occurrence of polycyclic aromatic hydrocarbons (PAH) in the environment Worldwide industrial and agricultural developments have released a large number of natural and synthetic hazardous compounds into the environment due to careless waste disposal, illegal waste dumping and accidental spills. As a result, there are numerous sites in the world that require cleanup of soils and groundwater. Polycyclic aromatic hydrocarbons (PAHs) are one of the major groups of these contaminants (Da Silva et al., 2003). PAHs constitute a diverse class of organic compounds consisting of two or more aromatic rings with various structural configurations (Prabhu and Phale, 2003). Being a derivative of benzene, PAHs are thermodynamically stable. In addition, these chemicals tend to adhere to particle surfaces, such as soils, because of their low water solubility and strong hydrophobicity, and this results in greater persistence under natural conditions. This persistence coupled with their potential carcinogenicity makes PAHs problematic environmental contaminants (Cerniglia, 1992; Sutherland, 1992). PAHs are widely found in high concentrations at many industrial sites, particularly those associated with petroleum, gas production and wood preserving industries (Wilson and Jones, 1993). 1.2 Remediation technologies Conventional techniques used for the remediation of soil polluted with organic contaminants include excavation of the contaminated soil and disposal to a landfill or capping - containment - of the contaminated areas of a site. These methods have some drawbacks. The first method simply moves the contamination elsewhere and may create significant risks in the excavation, handling and transport of hazardous material. Additionally, it is very difficult and increasingly expensive to find new landfill sites for the final disposal of the material. The cap and containment method is only an interim solution since the contamination remains on site, requiring monitoring and maintenance of the isolation barriers long into the future, with all the associated costs and potential liability. A better approach than these traditional methods is to completely destroy the pollutants, if possible, or transform them into harmless substances. Some technologies that have been used are high-temperature incineration and various types of chemical decomposition (for example, base-catalyzed dechlorination, UV oxidation). However, these methods have significant disadvantages, principally their technological complexity, high cost , and the lack of public acceptance. Bioremediation, on the contrast, is a promising option for the complete removal and destruction of contaminants. 1.3 Bioremediation of PAH contaminated soil & groundwater Bioremediation is the use of living organisms, primarily microorganisms, to degrade or detoxify hazardous wastes into harmless substances such as carbon dioxide, water and cell biomass Most PAHs are biodegradable unter natural conditions (Da Silva et al., 2003; Meysami and Baheri, 2003) and bioremediation for cleanup of PAH wastes has been extensively studied at both laboratory and commercial levels- It has been implemented at a number of contaminated sites, including the cleanup of the Exxon Valdez oil spill in Prince William Sound, Alaska in 1989, the Mega Borg spill off the Texas coast in 1990 and the Burgan Oil Field, Kuwait in 1994 (Purwaningsih, 2002). Different strategies for PAH bioremediation, such as in situ , ex situ or on site bioremediation were developed in recent years. In situ bioremediation is a technique that is applied to soil and groundwater at the site without removing the contaminated soil or groundwater, based on the provision of optimum conditions for microbiological contaminant breakdown.. Ex situ bioremediation of PAHs, on the other hand, is a technique applied to soil and groundwater which has been removed from the site via excavation (soil) or pumping (water). Hazardous contaminants are converted in controlled bioreactors into harmless compounds in an efficient manner. 1.4 Bioavailability of PAH in the subsurface Frequently, PAH contamination in the environment is occurs as contaminants that are sorbed onto soilparticles rather than in phase (NAPL, non aqueous phase liquids). It is known that the biodegradation rate of most PAHs sorbed onto soil is far lower than rates measured in solution cultures of microorganisms with pure solid pollutants (Alexander and Scow, 1989; Hamaker, 1972). It is generally believed that only that fraction of PAHs dissolved in the solution can be metabolized by microorganisms in soil. The amount of contaminant that can be readily taken up and degraded by microorganisms is defined as bioavailability (Bosma et al., 1997; Maier, 2000). Two phenomena have been suggested to cause the low bioavailability of PAHs in soil (Danielsson, 2000). The first one is strong adsorption of the contaminants to the soil constituents which then leads to very slow release rates of contaminants to the aqueous phase. Sorption is often well correlated with soil organic matter content (Means, 1980) and significantly reduces biodegradation (Manilal and Alexander, 1991). The second phenomenon is slow mass transfer of pollutants, such as pore diffusion in the soil aggregates or diffusion in the organic matter in the soil. The complex set of these physical, chemical and biological processes is schematically illustrated in Figure 1. As shown in Figure 1, biodegradation processes are taking place in the soil solution while diffusion processes occur in the narrow pores in and between soil aggregates (Danielsson, 2000). Seemingly contradictory studies can be found in the literature that indicate the rate and final extent of metabolism may be either lower or higher for sorbed PAHs by soil than those for pure PAHs (Van Loosdrecht et al., 1990). These contrasting results demonstrate that the bioavailability of organic contaminants sorbed onto soil is far from being well understood. Besides bioavailability, there are several other factors influencing the rate and extent of biodegradation of PAHs in soil including microbial population characteristics, physical and chemical properties of PAHs and environmental factors (temperature, moisture, pH, degree of contamination). Figure 1: Schematic diagram showing possible rate-limiting processes during bioremediation of hydrophobic organic contaminants in a contaminated soil-water system (not to scale) (Danielsson, 2000). 1.5 Increasing the bioavailability of PAH in soil Attempts to improve the biodegradation of PAHs in soil by increasing their bioavailability include the use of surfactants , solvents or solubility enhancers.. However, introduction of synthetic surfactant may result in the addition of one more pollutant. (Wang and Brusseau, 1993).A study conducted by Mulder et al. showed that the introduction of hydropropyl-ß-cyclodextrin (HPCD), a well-known PAH solubility enhancer, significantly increased the solubilization of PAHs although it did not improve the biodegradation rate of PAHs (Mulder et al., 1998), indicating that further research is required in order to develop a feasible and efficient remediation method. Enhancing the extent of PAHs mass transfer from the soil phase to the liquid might prove an efficient and environmentally low-risk alternative way of addressing the problem of slow PAH biodegradation in soil.

Seawater carbonate chemistry and biological processes of oysters Crassostrea virginica during experiments, 2010

Estuarine organisms are exposed to periodic strong fluctuations in seawater pH driven by biological carbon dioxide (CO2) production, which may in the future be further exacerbated by the ocean acidification associated with the global rise in CO2. Calcium carbonate-producing marine species such as mollusks are expected to be vulnerable to acidification of estuarine waters, since elevated CO2 concentration and lower pH lead to a decrease in the degree of saturation of water with respect to calcium carbonate, potentially affecting biomineralization. Our study demonstrates that the increase in CO2 partial pressure (pCO2) in seawater and associated decrease in pH within the environmentally relevant range for estuaries have negative effects on physiology, rates of shell deposition and mechanical properties of the shells of eastern oysters Crassostrea virginica (Gmelin). High CO2 levels (pH ~7.5, pCO2 ~3500 µatm) caused significant increases in juvenile mortality rates and inhibited both shell and soft-body growth compared to the control conditions (pH ~8.2, pCO2 ~380 µatm). Furthermore, elevated CO2 concentrations resulted in higher standard metabolic rates in oyster juveniles, likely due to the higher energy cost of homeostasis. The high CO2 conditions also led to changes in the ultrastructure and mechanical properties of shells, including increased thickness of the calcite laths within the hypostracum and reduced hardness and fracture toughness of the shells, indicating that elevated CO2 levels have negative effects on the biomineralization process. These data strongly suggest that the rise in CO2 can impact physiology and biomineralization in marine calcifiers such as eastern oysters, threatening their survival and potentially leading to profound ecological and economic impacts in estuarine ecosystems.

Irrigation efficiency and water-policy implications for river-basin resilience

Rising demand for food, fiber, and biofuels drives expanding irrigation withdrawals from surface water and groundwater. Irrigation efficiency and water savings have become watchwords in response to climate-induced hydrological variability, increasing freshwater demand for other uses including ecosystem water needs, and low economic productivity of irrigation compared to most other uses. We identify three classes of unintended consequences, presented here as paradoxes. Ever-tighter cycling of water has been shown to increase resource use, an example of the efficiency paradox. In the absence of effective policy to constrain irrigated-area expansion using "saved water", efficiency can aggravate scarcity, deteriorate resource quality, and impair river basin resilience through loss of flexibility and redundancy. Water scarcity and salinity effects in the lower reaches of basins (symptomatic of the scale paradox) may partly be offset over the short-term through groundwater pumping or increasing surface water storage capacity. However, declining ecological flows and increasing salinity have important implications for riparian and estuarine ecosystems and for non-irrigation human uses of water including urban supply and energy generation, examples of the sectoral paradox. This paper briefly considers three regional contexts with broadly similar climatic and water-resource conditions – central Chile, southwestern US, and south-central Spain – where irrigation efficiency directly influences basin resilience. The comparison leads to more generic insights on water policy in relation to irrigation efficiency and emerging or overdue needs for environmental protection.

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.