Biodegradation and environmental behavior of biodiesel mixtures in the sea: An initial study

Biodiesel, a mixture of fatty acid methyl esters (FAMEs) derived from animal fats or vegetable oils, is rapidly moving towards the mainstream as an alternative source of energy. However, the behavior of biodiesel, or blends of biodiesel with fossil diesel, in the marine environment have yet to be fully understood. Hence, we performed a series of initial laboratory experiments and simple calculations to evaluate the microbial and environmental fate of FAMEs. Aerobic seawater microcosms spiked with biodiesel or mixtures of biodiesel and fossil diesel revealed that the FAMEs were degraded at roughly the same rate as n-alkanes, and more rapidly than other hydrocarbon components. The residues extracted from these different microcosms became indistinguishable within weeks. Preliminary results from physical-chemical calculations suggest that FAMEs in biodiesel mixtures will not affect the evaporation rates of spilled petroleum hydrocarbons but may stabilize oil droplets in the water column and thereby facilitate transport.     

Marine debris review for Latin America and the wider Caribbean region: from the 1970s until now, and where do we go from here?

The available literature on marine debris from Latin America and the Wider Caribbean Region was collected and linked, reviewing their methodologies and principal results (quantities, composition and spatial-temporal patterns). The study region comprises 52 coastal countries of which only 14 had registers of works on marine debris. A total of 70 works were available and 69 had their full contents accessed. Brazil dominated the available literature with 70% of the documents. Beaches were the most studied environment, and plastics the prevalent form of contamination in the whole region. The exposure of marine biota (species, type of contact, consequences) was highlighted. The studied region, although still little exploited by this sort of research, shows the same contamination patterns observed world-wide. We also contacted 40 researchers in the area, collecting scientific contributions, opinions and suggestions for improvement of this research field. Further advances and new (urgently needed) lines of research are also discussed.     

Mass and flux distributions from DNAPL zones in sandy aquifers

At three industrial sites in Ontario, New Hampshire, and Florida, tetrachloroethylene (PCE) and trichloroethylene (TCE), released decades ago as dense nonaqueous phase liquids (DNAPLs), now form persistent source zones for dissolved contaminant plumes. These zones are suspended below the water table and above the bottoms of their respective, moderately homogeneous, unconfined sandy aquifers. Exceptionally detailed, depth-discrete, ground water sampling was performed using a direct-push sampler along cross sections of the dissolved-phase plumes, immediately downgradient of these DNAPL source zones. The total plume PCE or TCE mass-discharge through each cross section ranged between 15 and 31 kg/year. Vertical ground water sample spacing as small as 15 cm and lateral spacing typically between 1 and 3 m revealed small zones where maximum concentrations were between 1% and 61% of solubility. These local maxima are surrounded by much lower concentration zones. A spacing no larger than 15 to 30 cm was needed at some locations to identify high concentration zones, and aqueous VOC concentrations varied as much as four orders of magnitude across 30 cm vertical intervals. High-resolution sampling at these sites showed that three-quarters of the mass-discharge occurs within 5% to 10% of the plume cross sectional areas. The extreme spatial variability of the mass-discharge occurs even though the sand aquifers are nearly hydraulically homogeneous. Depth-discrete field techniques such as those used in this study are essential for finding the small zones producing most of the mass-discharge, which is important for assessing natural attenuation and designing remedial options.     

Effects of water use on arsenic release to well water in a confined aquifer

Field-based experiments were designed to investigate the release of naturally occurring, low to moderate (< 50 microg/L) arsenic concentrations to well water in a confined sandstone aquifer in northeastern Wisconsin. Geologic, geochemical, and hydrogeologic data collected from a 115 m2 site demonstrate that arsenic concentrations in ground water are heterogeneous at the scale of the field site, and that the distribution of arsenic in ground water correlates to solid-phase arsenic in aquifer materials. Arsenic concentrations in a test well varied from 1.8 to 22 microg/L during experiments conducted under no, low, and high pumping rates. The quality of ground water consumed from wells under typical domestic water use patterns differs from that of ground water in the aquifer because of reactions that occur within the well. Redox conditions in the well can change rapidly in response to ground water withdrawals. The well borehole is an environment conducive to microbiological growth, and biogeochemical reactions also affect borehole chemistry. While oxidation of sulfide minerals appears to release arsenic to ground water in zones within the aquifer, reduction of arsenic-bearing iron (hydr)oxides is a likely mechanism of arsenic release to water having a long residence time in the well borehole.     

Two-stage aquifer pumping subject to slow desorption and persistent sources

This work focuses on improving pump-and-treat remediation by optimizing a two-stage operational scheme to reduce volumes extracted when confronted with nonequilibrium desorption, low-permeability units, and continuous contaminant sources such as non-aqueous phase liquids (NAPL). Q1 and Q2 are the initial short-term high pumping rate and later long-term low pumping rate, respectively. A two-dimensional ground water flow and transport management model was used to test the proposed strategy for plumes developed from finite (NAPL-free) and continuous (NAPL-driven) contaminant sources in homogeneous and nonhomogeneous (zoned) aquifers. Remediation scenarios were simulated over durations of 2000, 6000, and 15,000 d to determine (1) the optimal time to switch from a preset Q1 to Q2 and (2) the value of Q2. The problem was constrained by mass removal requirements, maximum allowable downgradient concentrations, and practical bounds on Q2. Q1 was fixed at preset values 50% to 200% higher than the single-stage pumping rates (i.e., steady pumping rates during entire remediation period) necessary to achieve a desired cleanup level and capture the plume. Results for the NAPL-free homogeneous case under nonequilibrium desorption conditions achieved the same level of cleanup as single-stage pumping, while reducing extracted volumes by up to 36%. Comparable savings were obtained with NAPL-driven sources only when the source concentration was reduced by at least 2 orders of magnitude. For the zoned aquifer, the proposed strategy provided volume savings of up to 24% under NAPL-free and reduced source conditions.     

A sediment quality triad assessment of the impact of copper mine tailings disposal on the littoral sedimentary environment in the Atacama region of northern Chile

A sediment quality triad (SQT) assessment was made of the impact of copper mine tailings disposal on littoral meiofaunal assemblages in the Atacama region of northern Chile. This situation is unusual in that the disposal is direct into the high-energy coastal system and not via a river estuary or other low-energy environment. This situation also allows for the examination of the impact of copper mine tailings in the absence of confounding effects from other pollutants. The three components of the SQT were: 1. an analysis of the bioavailable metals in both the sedimentary porewater and the adjacent seawater, 2. a microcosm bioassay of both sediments and seawaters using meiofaunal assemblages, and 3. quantitative field samples of the meiofaunal assemblages. Twelve study sites with varying degrees of impact were used, including three reference sites. The study identified that both the meiofaunal assemblage densities and taxa diversities decrease with increasing levels of bioavailable copper, that the Foraminifera and Harpacticoida are sensitive to copper, and that otoplanid Turbellaria are often characteristic of impacted sites; tailings also have both chemical and physical impacts on the environment. In some cases the physical impact of tailings is more important in excluding some organisms e.g. the interstitial polychaete, Saccocirrus sonomacus, from a site than is their chemical impact.     

Spatial distribution and ecotoxicity of petroleum hydrocarbons in sediments from the Galicia continental shelf (NW Spain) after the Prestige oil spill

The distribution of aliphatic and aromatic hydrocarbons was determined in surface sediments collected at 36 stations along the Galicia continental shelf (NW Spain), following the Prestige oil spill. Sampling was performed in December 2002, just after the accident, and in February and September 2003. Concentrations of PAHs (summation operator 13 parent components) were in the range of 0.9-422 microg/kgdw, the highest values being close to coastal urban areas (e.g. Pontevedra and A Coru?a), whereas in the stations of the area most heavily impacted by the spill (off Costa da Morte) concentrations were in the range of 14.8-89.6 microg/kgdw, with a certain predominance of alkylated compounds, which may suggest a mixture of petrogenic and pyrolytic sources. The detailed study of petrogenic molecular markers (e.g. steranes and triterpanes) showed the occurrence of an old (weathered) petrogenic chronic pollution in the shelf sediments but not of the Prestige oil, with the possible exception of few stations in the area of Costa da Morte. This was attributed to the heavy nature of the spilled oil that was barely dispersed in the water column and mainly stranded on the coast or sedimented in the form of oil patches. The addition of increasing amounts of fuel oil to a representative sediment sample showed that the molecular indices were indicative of the presence of the Prestige oil when the amount was above 1g/kg of sediment. The toxicity of selected samples (showing the higher PAH concentrations) was tested using the bivalve embryogenesis bioassay. Embryogenesis success reached high values in all cases (80-88%, with 86% in the control), indicating a lack of toxicity in the sediments and supporting the conclusion that the patchiness of the fuel eventually reaching the seafloor reduced its impact on the benthic communities of the Galician shelf.     

Influence of the oceanographic conditions during spring 2003 on the transport of the Prestige tanker fuel oil to the Galician coast

Hydrographic data collected during the cruise HIDROPRESTIGE were combined with meteorological and dynamic data provided by remote sensors and drifting/moored buoys, to describe the surface circulation of the Northern Iberian basin in March-April 2003. Sea surface winds transported the floating Prestige oil slicks from the sinking area to the continental slope off the Rías Baixas in 1/2 month: the surface current intensity was 2% of the wind intensity and it was rotated clockwise 5 degrees from the wind direction. Mesoscale cyclonic and anticyclonic structures west of 10 degrees W increased the residence time of oil patches in the Northern Iberian basin, as compared with the expected southwards flow of the Iberian current (IC). On the other hand, the Iberian poleward current (IPC) formed a marked surface front with coastal waters, preventing the entry of fuel oil into the rías. PAHs in the surface layer during the cruise were <0.5 microgL(-1), except in the Galicia bank (approximately 1 microg L(-1); where the Prestige tanker was still leaking) and the vicinity of Cape Fisterra (approximately 1.5 microg L(-1); where the convergence front between the IPC and coastal waters vanished).