Milena Fernandes

Characterization of carbonaceous combustion residues. I. Morphological, elemental and spectroscopic features

Scanning electron microscopy, surface area determination, elemental analysis, organic matter extraction and solid-state cross polarization/magic angle spinning and Bloch decay/magic angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy were used to investigate distinctive features among carbonaceous combustion residues. Black carbon (BC) samples included diesel soot, urban dust, carbon black, chimney soot, vegetation fire residues, wood and straw charcoals. Particles varied from small spheres (<50 nm) in fossil BC (>100 m(2)/g), to large layered structures in plant-derived BC (generally <8 m(2)/g). Chimney soot also included large (>1 micrometer) liquid-like structures, while spherules >100 nm were unique to urban dust. The ratios of amorphous to soot carbon (SC) (isolated by thermal degradation) were not necessarily correlated with the degree of aromaticity estimated from H/C ratios. In particular, values of SC in diesel soot were clearly overestimated. Solvent-extractable organic matter (SEOM) was <2% for charcoals and carbon black, but >13% for urban dust, chimney and diesel soot. SEOM is thought to clog pores or to form large waxy globules, hence reducing surface areas. The ratio of polar/nonpolar SEOM was generally <7 for fossil BC, but >30 for plant-derived BC. NMR analysis revealed essentially one chemical shift in the aromatic C region of charcoals, while diesel soot also showed important aliphatic contributions. Aliphatic and oxygenated C predominated over aryl C in urban dust and chimney soot. These morphological and chemical characteristics of the BC samples are discussed in terms of their environmental implications.

How does acid treatment to remove carbonates affect the isotopic and elemental composition of soils and sediments

Environmental context. The ability to accurately determine the elemental and isotopic composition of soils and sediments has important implications to our quantitative understanding of global biogeochemical cycles. However, the analysis of organic carbon in solid matrices is a time-consuming task that requires the selective removal of carbonates, a treatment that has the potential to significantly alter the composition of the original sample. In the present work, we compare three of the most common acid treatments used for carbonate removal, and critically evaluate their effect on the content and isotopic signature of organic carbon and nitrogen in both soils and sediments. Abstract. In the present work, we compared the efficacy of three acid treatments in removing carbonates from soils and sediments for elemental and isotopic analysis. The methods tested were (1) refluxing with H2SO3; (2) in situ treatment with H2SO3 in silver capsules; and (3) treatment with HCl followed by rinsing with water. Refluxing with H2SO3 led to substantial losses of organic carbon and nitrogen, but comparatively small nitrogen isotopic shifts. The in situ treatment was inadequate for carbonate-rich samples (contents ≥30%) as a consequence of the formation of a mineral precipitate. Treatment with HCl led to substantial losses of nitrogen from carbonate-rich samples, and deviations in nitrogen isotopic signatures (δ15N) of up to 3.7‰. δ15N values showed no significant difference between acid-treated and untreated samples or between treatments, although variability was high and influenced by sample composition. Carbonate-poor samples showed no statistical difference in δ13C values between treatments, whereas carbonate-rich samples tended to be more 13C-depleted when treated with HCl, potentially suggesting the preferential preservation of 13C-depleted compounds (e.g. lipids or lignin).

Poly-aromatic hydrocarbon (PAH) inputs from the Rhône River to the Mediterranean Sea in relation with the hydrological cycle: Impact of floods

The concentrations of dissolved and particulate polycyclic aromatic hydrocarbons (PAHs) were monitored in waters of the Rhône River (France) every fortnight for a full calendar year, from June 1994 to May 1995. All flood events occurring over the course of the experiment were sampled at higher frequency to better quantify the impact of these extreme hydrological episodes on the annual export of PAHs to the Mediterranean Sea. This time-series indicates that more than 90% of the annual load of particulate PAHs is transported during flood episodes, with 77% discharged during the course of only one extreme flood event occurring in November 1994. During these intense events, riverine particles are depleted in PAHs while at low river discharge particles are PAH-enriched. Dissolved PAHs were less variable and less abundant than adsorbed PAHs, consistently with the low solubility of these compounds.

Bioconcentration of triclosan and methyl-triclosan in marine mussels (Mytilus galloprovincialis) under laboratory conditions and in metropolitan waters of Gulf St Vincent, South Australia

The anti-microbial agent triclosan (TCS), and its derivative methyl-triclosan (Me-TCS), are discharged with treated effluents from wastewater treatment plants to receiving environments. We investigated the bioconcentration of TCS and Me-TCS in mussels (Mytilus galloprovincialis) exposed to TCS (100 ng L(-1)) for 30 days in seawater aquaria (19±2°C) with fresh phytoplankton as a food source. Bioconcentration increased with time reaching a steady-state around 24-30 days. The bioconcentration factor (log BCF) for TCS were 2.81 L kg(-1) (dry weight) and 4.13 L kg(-1), when lipid normalised concentrations were used. Mussels were also deployed in cages at four marine locations receiving effluents from WWTPs. The mean (±SD) TCS and Me-TCS concentrations for mussels from these sites were 9.87 (±1.34) and 6.99 (±2.44) μg kg(-1). The study showed that mussels can be a useful tool for monitoring pollution of TCS and Me-TCS in marine and estuarine environments.

Testing for thresholds of ecosystem collapse in seagrass meadows

Although the public desire for healthy environments is clear-cut, the science and management of ecosystem health has not been as simple. Ecological systems can be dynamic and can shift abruptly from one ecosystem state to another. Such unpredictable shifts result when ecological thresholds are crossed; that is, small cumulative increases in an environmental stressor drive a much greater change than could be predicted from linear effects, suggesting an unforeseen tipping point is crossed. In coastal waters, broad-scale seagrass loss often occurs as a sudden event associated with human-driven nutrient enrichment (eutrophication). We tested whether the response of seagrass ecosystems to coastal nutrient enrichment is subject to a threshold effect. We exposed seagrass plots to different levels of nutrient enrichment (dissolved inorganic nitrogen) for 10 months and measured net production. Seagrass response exhibited a threshold pattern when nutrient enrichment exceeded moderate levels: there was an abrupt and large shift from positive to negative net leaf production (from approximately 0.04 leaf production to 0.02 leaf loss per day). Epiphyte load also increased as nutrient enrichment increased, which may have driven the shift in leaf production. Inadvertently crossing such thresholds, as can occur through ineffective management of land-derived inputs such as wastewater and stormwater runoff along urbanized coasts, may account for the widely observed sudden loss of seagrass meadows. Identification of tipping points may improve not only adaptive-management monitoring that seeks to avoid threshold effects, but also restoration approaches in systems that have crossed them.