Copper complexes as a source of redox active MRI contrast agents

The study reports an advance in designing copper-based redox sensing MRI contrast agents. Although the data demonstrate that copper(II) complexes are not able to compete with lanthanoids species in terms of contrast, the redox-dependent switch between diamagnetic copper(I) and paramagnetic copper(II) yields a novel redox-sensitive contrast moiety with potential for reversibility.

Hydroxyl radical generation by cactus-like copper oxide nanoporous carbon catalysts for microcystin-LR environmental remediation

Copper oxide supported on nanoporous activated carbon (CuO-NPAC) is reported for the aqueous phase catalytic degradation of cyanotoxin microcystin-LR (MC-LR). The loading and spatial distribution of CuO throughout the NPAC matrix strongly influence the catalytic efficiency. CuO-NPAC synthesis was optimized with respect to the copper loading and thermal processing, and the physicochemical properties of the resulting materials were characterized by XRD, BET, TEM, SEM, EPR, TGA, XPS and FT-IR spectroscopy. EPR spin trapping and fluorescence spectroscopy showed in situ ˙OH formation via H2O2 over CuO-NPAC as the catalytically relevant oxidant. The impact of reaction conditions, notably CuO-NPAC loading, H2O2 concentration and solution pH, is discussed in relation to the reaction kinetics for MC-LR remediation.

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).

Industrial Discharges of Metals in Kigali, Rwanda, and the Impact on Drinking Water Quality

Rwanda is a landlocked country located in Africa's Central-East Great Lakes region. It has a population of 7.5 million which occupies 26,338 km'. Its population density (285/km') is one of the highest in the world and has prompted fear of a rapid degradation of the ecosystem. There are no central sewer systems in Rwanda. The use of pit latrines and septic tanks is common in urban and rural areas. People still defecate in the fields (World Bank, 1989). Less than half of the urban population is served by a central water supply. The majority of people get their water untreated from rivers that have been polluted by chemicals and human excreta. In and around the capital city of Kigali, there is a concentration of people, farms, and industries which discharge wastewater into the Nyabarongo River and its tributaries. The Nyabarongo River, a tributary of the Nile, empties into the Akagera River which flows into Lake Victoria. Nyabarongo River water is used for drinking water, cooking, bathing, and agriculture in the Kigali area. There has been very little monitoring of the water quality of the Nyabarongo River and of industrial outfalls located on tributaries of the Nyabarongo River. As a first step in understanding the water quality of the Nyabarongo River, wastewater samples were collected in 1993 from industrial outfalls located on tributaries of the Nyabarongo River. Most of the facilities sampled had no wastewater treatment. The impact of these discharges on the water quality of the Nyabarongo River was evaluated.

Formation and investigation of nanostructured thin films

Small devices, in the range of nanometers, are playing a major role in today's technology. The field of nanotechnology is concerned with materials and systems whose structures and components exhibit novel and significantly improved physical, chemical and biological properties, phenomena and processes due to their small nanoscale size. Researches more and more are finding that structural features in the range of about 1 to 100 nanometers behave quite differently than isolated molecules (1 nanometer) or bulk materials. For comparison, a 10 nanometer structure is 1000 times smaller than the diameter of a human hair. The virtues of working in the nanodomain are increasingly recognized by the scientific community and discussed in the popular press. The use of such devices is expected to revolutionize our industries and lives. ^ This work mainly focuses on the fabrication, characterization and discovery of new nanostructured thin films. This research consists of the design of a new high-deposition rate nanoparticle machine for depositing nanostructured films from beams of nanoparticles and investigation film's unique optical and physical properties.^ A high-deposition rate nanoparticle machine was designed, built and successfully tested. Different nanostructured thin films were deposited from Copper, Gold, Iron and Zirconium targets with the grain size of between 1 to 20 nm under different conditions. Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), and x-ray diffraction (XRD) confirmed nanoscale grain size structures of deposited films. The optical properties of the nanostructured films deposited from copper, Iron and Zirconium targets were significantly different from optical properties of bulk and thin films. Zr, Cu and Fe films were transparent. Gold films revealed an epitaxial contact with the silicon substrate with interesting crystal structures. ^ The new high-deposition rate nanoparticle machine was able to deposit new nanostructured films with different properties from bulk and thin films reported in the literatures. ^

Occurrence and environmental fate of Irgarol 1051, a new antifouling agent

The purpose of this study is to characterize the degradation products of Irgarol 1051(2-methylthio-4-tertbutylamino-6-cyclopropylamino- s-triazine), a compound recently developed for use as an antifouling agent on boat hulls. The photolytic fate of this compound in different natural waters will be used in the development of a monitoring program designed to survey the occurrence of this compound and its degradation products in South Florida marinas, the Miami River and surrounding coastal areas. ^ The transformation of Irgarol 1051 and degradation rate constants were characterized in a photo-reactor under simulated natural conditions. The degradation pathway in the UVB-UVA region (300nm to 350nm) closely resembled the transformations under natural conditions in the pond, showing that both direct photolysis and the presence of natural sensitizers play an important role in the abiotic transformation of this compound. Irgarol 1051 has an average environmental half-life of 10 days in surface waters. Average concentrations from samples around Biscayne Bay and the Miami River increased from 1–5 ng/L during 1999 and increased to between 28 and 38 ng/L in 2001, respectively. Irgarol concentrations showed a strong correlation with concentrations of its major transformation product, M1, from samples collected as part of the study ([M1]/[Irgarol] = 0.247, R2 = 0.9165, n = 125). ^

Assessing the sources, quantities, and trends on human waste contamination along protected south Florida ecosystem: A chemical tracer based study

The common occurrence of human derived contaminants like pharmaceuticals, steroids and hormones in surface waters has raised the awareness of the role played by the release of treated or untreated sewage in the water quality along sensitive coastal ecosystems. South Florida is home to many important protected environments ranging from wetlands to coral reefs which are in close proximity to large metropolitan cities. Since large portions of South Florida and most of the Florida Keys population are not served by modern sewage treatment plants and rely heavily on the use of inefficient septic systems; a comprehensive survey of selected human waste contamination markers is needed in these areas to assess water quality with respect to non-traditional micro-constituents. ^ This study reports the development and application of new sensitive and selective analytical methods for the fast screening of multiple wastewater tracers, classified as Emergent Pollutants of Concern (EPOC). Novel methods for the trace analysis of non-traditional markers of human-specific contamination such as aminopropanone were developed and used to assess the potential of non-traditional markers as wastewater tracers. ^ During our investigation, surface water samples collected from near shore environments along the South Florida were analyzed for fifteen hormones and steroids, and five commonly detected pharmaceuticals. The compounds most frequently detected were: coprostanol, cholesterol, estrone, β-estradiol, caffeine, triclosan and DEET. Concentrations of caffeine, bisphenol A and DEET were usually higher and more prevalent than the hormonal steroids. In general, it was found that common pharmaceuticals and steroids are widely present in major coastal environments in South Florida. It is also evident that aquatic bodies in heavily urbanized sectors such as the Miami River and Key Largo Harbor contain higher concentrations of several compounds while relatively open bay waters and agricultural areas show reduced chemical signatures. Concentrations of hormones in the Little Venice area of Marathon Key were above the Lowest Observable Effect Levels (LOELs) for several species, indicating that biological resources in this area are at risk. Water quality issues in some of these coastal water environments go beyond eutrophication, thus EPOC should be the target goal for future mitigation projects. ^

Shifting N and P limitation along a north-south gradient of mangrove estuaries in South Florida

A multivariate statistical analysis was applied to a 10 year, multiparameter data set in an effort to describe the spatial dependence and inherent variation of water quality patterns in the mangrove estuaries of Ten Thousand Islands – Whitewater Bay area. Principal component analysis (PCA) of 16 water quality parameters collected monthly resulted in five groupings, which explained 72.5% of the variance of the original variables. The “Organic” component (PCI) was composed of alkaline phosphatase activity, total organic nitrogen, and total organic carbon; the “Dissolved Inorganic N” component (PCII) contained NO 3 − , NO 2 − , and NH 4 + ; the “Phytoplankton” component (PCIII) was made up of total phosphorus, chlorophyll a, and turbidity; dissolved oxygen and temperature were inversely related (PCIV); and salinity and soluble reactive phosphorus made up PCV. A cluster analysis of the mean and SD of PC scores resulted in the spatial aggregation of the 47 fixed stations into six classes having similar water quality, which we defined as: Mangrove Rivers, Whitewater Bay, Gulf Islands, Coot Bay, Blackwater River, and Inland Waterway. Marked differences in physical, chemical, and biological characteristics among classes were illustrated by this technique. Comparison of medians and variability of parameters among classes allowed large scale generalizations as to underlying differences in water quality in these regions. A strong south to north gradient in estuaries from high N - low P to low N - high P was ascribed to marked differences in landuse, freshwater input, geomorphology, and sedimentary geology along this tract. The ecological significance of this gradient discussed along with potential effects of future restoration plans.

Salinity and Chlorophyll a as Performance Measures to Rehabilitate a Mangrove-Dominated Deltaic Coastal Region: the Ciénaga Grande de Santa Marta–Pajarales Lagoon Complex, Colombia

Salinity, water temperature, and chlorophyll a (chl-a) biomass were used as performance measures in the period 1999–2001 to evaluate the effect of a hydrological rehabilitation project in the Ciénaga Grande de Santa Marta (CGSM)–Pajarales lagoon complex, Colombia where freshwater diversions were initiated in 1995 and completed in 1998. The objective of this study was to evaluate how diversions of freshwater into previously hypersaline (>80) environments changed the spatial and temporal distribution of environmental characteristics. Following the diversion, 19 surveys and transects using a flow-through system were surveyed in the CGSM–Pajarales complex to continuously measure selected water quality parameters. Geostatistical analysis indicates that hydrology and salinity regimes and water circulation patterns in the CGSM lagoon are largely controlled by freshwater discharge from the Fundacion, Aracataca, and Sevilla Rivers. Residence times in the CGSM lagoon were similar before (15.5 ± 3.8 days) and after (14.2 ± 2.0 days) the rehabilitation project and indicated that the system is flushed regularly. In contrast, chl-a biomass was highly variable in the CGSM–Pajarales lagoon complex and not related to discharge patterns. Mean annual chl-a biomass (44–250 μg L−1) following the diversion project was similar to values recorded since the 1980s and still remains among the highest reported in coastal systems around the world owing to its unique hydrology regulated by the Magdalena River and Sierra Nevada de Santa Marta watersheds and the high teleconnection to the El Niño Southern Oscillation (ENSO). Our results confirm that the reduction in salinity in the CGSM lagoon and Pajarales complex during 1999–2000 was largely driven by high precipitation (2500 mm) induced by the ENSO–La Niña rather than by the freshwater diversions.

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.

Terrigenous biomarker proxies analysed in the Amazon River system

Paleoenvironmental studies based on terrigenous biomarker proxies from sediment cores collected close to the mouth of large river systems rely on a proper understanding of the processes controlling origin, transport and deposition of biomarkers. Here, we contribute to the understanding of these processes by analyzing long-chain n-alkanes from the Amazon River system. We use the dD composition of long-chain n-alkanes from river bed sediments from the Amazon River and its major tributaries, as well as marine core-top samples collected off northeastern South America as tracers for different source areas. The d13C composition of the same compounds is used to differentiate between long-chain n-alkanes from modern forest vegetation and petrogenic organic matter. Our d13C results show depleted d13C values (-33 to -36 per mil) in most samples, indicating a modern forest source for most of the samples. Enriched values (-31 to -33 per mil) are only found in a few samples poor in organic carbon indicating minor contributions from a fossil petrogenic source. Long-chain n-alkane dD analyses show more depleted values for the western tributaries, the Madeira and Solimões Rivers (-152 to -168 per mil), while n-alkanes from the lowland tributaries, the Negro, Xingu and Tocantins Rivers (-142 to -154 per mil), yield more enriched values. The n-alkane dD values thus reflect the mean annual isotopic composition of precipitation, which is most deuterium-depleted in the western Amazon Basin and more enriched in the eastern sector of the basin. Samples from the Amazon estuary show a mixed long-chain n-alkane dD signal from both eastern lowland and western tributaries. Marine core-top samples underlying the Amazon freshwater plume yield dD values similar to those from the Amazon estuary, while core-top samples from outside the plume showed more enriched values. Although the variability in the river bed data precludes quantitative assessment of relative contributions, our results indicate that long-chain n-alkanes from the Amazon estuary and plume represent an integrated signal of different regions of the onshore basin. Our results also imply that n-alkanes are not extensively remineralized during transport and that the signal at the Amazon estuary and plume includes refractory compounds derived from the western sector of the Basin. These findings will aid in the interpretation of plant wax-based records of marine sediment cores collected from the adjacent ocean.

(Tables 1-3) Water chemistry of cloud forest streams at baseflow conditions, Rio San Francisco, Ecuador

We investigated controls on the water chemistry of a South Ecuadorian cloud forest catchment which is partly pristine, and partly converted to extensive pasture. From April 2007 to May 2008 water samples were taken weekly to biweekly at nine different subcatchments, and were screened for differences in electric conductivity, pH, anion, as well as element composition. A principal component analysis was conducted to reduce dimensionality of the data set and define major factors explaining variation in the data. Three main factors were isolated by a subset of 10 elements (Ca2+, Ce, Gd, K+, Mg2+, Na+, Nd, Rb, Sr, Y), explaining around 90% of the data variation. Land-use was the major factor controlling and changing water chemistry of the subcatchments. A second factor was associated with the concentration of rare earth elements in water, presumably highlighting other anthropogenic influences such as gravel excavation or road construction. Around 12% of the variation was explained by the third component, which was defined by the occurrence of Rb and K and represents the influence of vegetation dynamics on element accumulation and wash-out. Comparison of base- and fast flow concentrations led to the assumption that a significant portion of soil water from around 30 cm depth contributes to storm flow, as revealed by increased rare earth element concentrations in fast flow samples. Our findings demonstrate the utility of multi-tracer principal component analysis to study tropical headwater streams, and emphasize the need for effective land management in cloud forest catchments.

Raw X-ray fluorescence (XRF) scannings and radiocarbon age of sediment cores GeoB8331-4, and GeoB8322-2

Variations in the sediment input to the Namaqualand mudbelt during the Holocene are assessed using an integrative terrestrial to marine, source to sink approach. Geochemical and Sr and Nd isotopic signatures are used to distinguish fluvial sediment source areas. Relative to the sediments of the Olifants River, craton outcrops in the northern Orange River catchment have a more radiogenic Sr and a more unradiogenic Nd isotopic signature. Furthermore, upper Orange River sediments are rich in heavier elements such as Ti and Fe derived from the chemical weathering of Drakensberg flood basalt. Suspension load signatures change along the Orange River's westward transit as northern catchments contribute physical weathering products from the Fish and Molopo River catchment area. Marine cores offshore of the Olifants (GeoB8323-2) and Orange (GeoB8331-4) River mouths show pulses of increased contribution of Olifants River and upper Orange River input, respectively. These pulses coincide with intervals of increased terrestrial organic matter flux and increased paleo-production at the respective core sites. We attribute this to an increase in fluvial activity and vegetation cover in the adjacent catchments during more humid climate conditions. The contrast in the timing of these wet phases in the catchment areas reflects the bipolar behavior of the South African summer and winter rainfall zones. While rainfall in the Orange River catchment is related to southward shifts in the ICTZ, rainfall in the Olifants catchment is linked to northward shifts in Southern Hemisphere Westerly storm tracks. The later may also have increased southern Benguela upwelling in the past by reducing the shedding of Agulhas eddies into the Atlantic. The high-resolution records of latitudinal shifts in these atmospheric circulation systems correspond to late Holocene centennial-millennial scale climate variability evident in Antarctic ice core records. The mudbelt cores indicate that phases of high summer rainfall zone and low winter rainfall zone humidity (at ca. 2.8 and 1 ka BP) may be synchronous with Antarctic warming events. On the other hand, dry conditions in the summer rainfall zone along with wet conditions in the winter rainfall zone (at ca 3.3, 2 and 0.5 ka BP) may be associated with Antarctic cooling events.

Ajustes de coeficientes integrantes de processos físicos e bioquímicos na autedepuração em curso de água de médio porte

The mathematical modeling in the simulation of self-purification capacity in lotic environment is an important tool in the planning and management of hydric resources in hydrographic basin scale. It satisfactorily deals with the self-purification process when the coefficients of physical and biochemical processes are calibrated from monitorated water quality data, which was the main focus of this study. The present study was conducted to simulate the behavior of the parameters OD, BOD5, total phosphorus, E. coli, ammonia, nitrite, nitrate and the total metals cadmium, chromium, copper, lead and zinc in the Uberabinha’s lower course (with an approximate annual growth flow between 4-35 m3/s), in a stretch of 19 km downstream of the treated effluent release by the WWTP of the city. The modelings, on the present study, show the importance of constant water quality parameters monitoration over the water course, based on the comparison of the simulations from calibrated coefficients and coefficients obtained in the literature for the period of June until November 2015. After coefficients calibration, there were good adjustments between simulated and measured data for the parameters OD, BOD, Ptotal, ammonia and nitrate and unsatisfactory adjust for the parameters nitrite and E. coli. About the total metals, the adjustments were not satisfactory on the reservoir’s vicinity of the Small Hydropower Plant Martins, due the considerable increase of the bottom sediment in lentic region. The greatest scientific contribution of this study was to calibrate the decay coefficient K and the quantification of the release by the fund S of total metals in watercourse midsize WWTP pollutant load receptor, justified by the lack of studies in the literature about the subject. For the metals cadmium, chromium, copper, lead and zinc, the borderline for K and S calibrated were: 0.0 to 13.0 day-1 and 0.0 to 1.7 g/m3.day; 0.0 to 0.9 day-1 and 0.0 to 7.3 g/m3.day; 0.0 to 25.0 day-1 and 0.0 to 1.8 g/m3.day; 0.0 to 7.0 day-1 and 0.0 to 40.3 g/m3.day; 0.0 to 30.0 day-1 and 0.0 to 70.1 g/m3.day.