The effects of crude oil and the effectiveness of cleaner application following oiling on US Gulf of Mexico coastal marsh plants

Field studies were conducted in two different marsh habitats in Louisiana coastal wetlands to evaluate the effects of oiling (using South Louisiana Crude oil, SLC) and the effectiveness of a shoreline cleaner (COREXIT 9580) in removing oil from plant canopies. The study sites represented two major marsh habitats; the brackish marsh site was covered by Spartina patens and the freshwater marsh was covered by Sagittaria lancifolia. Field studies were conducted in each habitat using replicated 5.8 m2 plots that were subjected to three treatments; oiled only, oiled + cleaner (cleaner was used 2 days after oiling), and a control. Plant gas exchange responses, survival, growth, and biomass accumulation were measured. Results indicated that oiling led to rapid reductions in leaf gas exchange rates in both species. However, both species in 'oiled + cleaned' plots displayed improved leaf conductance and CO2 fixation rates. Twelve weeks after treatment initiation, photosynthetic carbon fixation in both species had recovered to normal levels. Over the short-term, S. patens showed more sensitivity to oiling with SLC than S. lancifolia as was evident from the data of the number of live shoots and above-ground biomass. Above-ground biomass remained significantly lower than control in S. patens under 'oiled' and 'oiled + cleaned' treatments while it was comparable to controls in S. lancifolia. These studies indicated that the cleaner removed oil from marsh grasses and alleviated the short-term impact of oil on gas exchange function of the study plants. However, use of cleaner had no detectable effects on above-ground biomass production or regeneration at the end of the first growing season in S. patens. Similarly, no beneficial effects of cleaner on carbon fixation and number of live shoots were apparent beyond 12 weeks in S. lancifolia.     

Evaluation of alternative oil spill cleanup techniques in a Spartina alterniflora salt marsh

Three oil spill situations which cause long-term impact were simulated in 1 m(2) salt marsh plots to evaluate the effectiveness of alternative cleanup techniques at removing oil and reducing damage to Spartina alterniflora. Cleanup techniques, implemented 18-24 h after oiling, were not effective at removing oil after sediment penetration. When oil remained on the sediment surface, flushing techniques were most effective at removal, reducing levels of added oil by 73% to 83%. The addition of dispersant to the flushing stream only slightly enhanced oil removal. Clipping of vegetation followed by sorbent pad application to sediment was moderately effective, reducing added oil by 36% to 44%. In contrast to flushing and clipping, burning increased the amount of oil in sediment by 27% to 72%. Although flushing and clipping were effective at oil removal, neither technique reduced initial damage to plants or enhanced long-term recovery. While flushed plots sustained no additional plant damage due to cleanup, clipped and burned plots sustained additional initial plant damage. Based on these results, first considerations should be given to natural tidal flushing as the means to remove oil, especially in salt marshes subject to ample tidal inundation. Although our results do not support cleanup in salt marshes with ample tidal inundation, low pressure flushing may be warranted when fuel oils or large quantities of crude oil impact salt marshes subject to reduced tidal flushing. Flushing, when warranted, should be initiated prior to oil penetration into the substrate. Clipping may be considered as a cleanup response only when heavy oil cannot be effectively removed from vegetation by flushing. Burning is not recommended because it enhances oil penetration into sediment and causes substantial initial plant damage.     

Impact of permanent inundation on methane emissions from a Spartina alterniflora coastal salt marsh

To understand the effect of water level on CH₄ emissions from an invasive Spartina alterniflora coastal brackish marsh, we measured CH₄ emissions from intermittently and permanently (5 cm water depth) inundated mesocosms with or without N fertilizer added at a rate of 2.7 g N m^?2. Dissolved CH₄ concentrations in porewater and vertically-profiled sediment redox potential were measured, as were aboveground biomass and stem density of S. alterniflora. Mean CH₄ fluxes during the growing season in permanently inundated mesocosms without and with N fertilizer were 1.03 and 1.73 mg CH₄ m^?2 h^?1, respectively, which were significantly higher than in the intermittently inundated mesocosms. This response indicates that prolonged submergence of sediment, up to a water depth of 5 cm, stimulated CH₄ release. Inundation did not greatly affect aboveground biomass and stem density, but did significantly reduce redox potential in sediment, which in turn stimulated CH₄ production and increased the CH₄ concentration of porewater, resulting in higher CH₄ emission in the mesocosm. Our data showed that the stimulatory effect of shallow, permanent inundation on CH₄ emission in S. alterniflora marsh sediment was due primarily to an improved methanogenic environment rather than an increase in plant-derived substrates and/or the number of gas emission pathways through the plant’s aerenchymal system.     

The effects of oil spill and clean-up on dominant US Gulf coast marsh macrophytes: a review

The objective of this review was to synthesize existing information regarding the effects of petroleum hydrocarbons on marsh macrophytes in a manner that will help guide research and improve spill-response efficiency. Petroleum hydrocarbons affect plants chemically and physically. Although plants sometime survive fouling by producing new leaves, even relatively non-toxic oils can stress or kill plants if oil physically prevents plant gas-exchange. Plant sensitivity to fouling varies among species and among populations within a species, age of the plant, and season of spill. Physical disturbance and compaction of vegetation and soil associated with clean-up activities following an oil spill appear to have detrimental effects on the US Gulf coast marshes. Other techniques, including the use of chemicals such as cleaners or bioremediation, may be necessary to address the problem. Clean-up may also be beneficial when timely removal prevents oil from migrating to more sensitive habitats.     

The effect of crude oil and oil spill chemicals on nitrogen fixation in the cyanobacteria Nostoc sp

The effects of crude oil and three oil spill dispersants (Corexit 9600, 9550 and 7664) on nitrogenase activity in the cyanobacteria Nostoc sp. were examined. The addition of oil to Nostoc sp. cultures resulted in a catastrophic decline in nitrogenase activity with activity ceasing 7 h after treatment. The addition of a dispersant with the oil did not ameliorate this effect. Cultures exposed to high concentrations of dispersants showed lower rates on nitrogenase activity than untreated cultures. However, it is unlikely that dispersant concentrations of this magnitude would occur in the field. At the lowest concentration tested, which approximates the manufacturer's recommended application rate, the effects of the dispersant appear to be negligible.     

Impact of a massive crude oil spill on the invertebrate fauna of a Missouri Ozark stream

The benthic macroinvertebrate fauna of Asher Creek, a 4th order stream with a base flow of 0.03 m(3)/s, was monitored on 11 occasions for 532 days following a 1.5 million liter domestic crude oil spill. Aquatic insects, crustaceans, segmented worms, roundworms, flatworms, snails, freshwater mussels and other benthic organisms in the oil impacted area were reduced to less than 0.1% of expected numbers at the first sampling period 25 days after the spill. Species diversity indices and the number of mayfly and stonefly taxa were less than the minimum values established for unpolluted Missouri streams for 11 months. The initial post-spill community was dominated by Chironomidae (midges), Simuliidae (blackflies) and Oligochaeta (segmented worms). Some species of Plecoptera (stoneflies), Ephemeroptera (mayflies) and Trichoptera (caddisflies) were absent from the fauna for as long as 9 months. The functional feeding groups of scrapers, filterers, gatherers, and predators initially decreased in relative abundance. Predators later increased in response to a rapidly expanding prey base. Shredders did not change in relative abundance throughout the recovery period. Oil was visually present in the stream riffle substrate for 453 days following the spill. Dissolved oxygen, pH and conductivity were not affected. The visible appearance of oil in the stream substrate was a simple predictor of the status of the benthic invertebrate community. Areas protected with surface skimming siphon dams were less severely impacted and recovered more rapidly than areas where the stream substrate was inundated with oil. The most apparent factors controlling the recovery were the total volume of water passing through the contaminated area and the occurrence of scouring flood.     

Effect of crude oil contaminated sediment exposure on cytochrome P450 enzymes in the Australian asteroid Coscinasterias muricata

Levels of cytochrome P450 enzymes were measured in pyloric caeca microsomes of the asteroid Coscinasterias muricata following exposure to sediment with nominal concentrations of 0, 0.1 or 2 ml crude oil kg(-1) (dry weight) and subsequent depuration. No significant differences were observed in total cytochrome P450 levels or cytochrome P418 levels following the exposure period. However after five days of depuration, levels of total P450 in the pyloric caeca of C. muricata exposed to the highest oiled sediment concentration were significantly lower than in specimens exposed to the other treatments. Cytochrome P418 levels were inversely related to total P450 levels following exposure and subsequent depuration. Preliminary results show that levels of CYP1A-like immunopositive protein (CYP1A-like IPP) in exposed asteroids exhibited a concentration response relationship following the exposure period. Variations in CYP1A-like IPP levels observed during the depuration period may be influenced by the sublethal toxicity of hydrocarbons within the crude oil.     

GC and GC-MS characterization of crude oil transformation in sediments and microbial mat samples after the 1991 oil spill in the Saudi Arabian Gulf coast

The massive oil discharge in the Saudi Arabian coast at the end of the 1991 Gulf War is used here as a natural experiment to study the ability of microbial mats to transform oil residues after major spills. The degree of oil transformation has been evaluated from the analysis of the aliphatic and aromatic hydrocarbons by gas chromatography (GC) and GC coupled to mass spectrometry (GC-MS). The oil-polluted microbial mat samples from coastal environments exhibited an intermediate degree of transformation between that observed in superficial and deep sediments. Evaporation, photo-oxidation and water-washing seemed to lead to more effective and rapid elimination of hydrocarbons than cyanobacteria and its associated microorganisms. Furthermore, comparison of some compounds (e.g. regular isoprenoid hydrocarbons or alkylnaphthalenes) in the oil collected in the area after the spill or in the mixtures retained by cyanobacterial growth gave rise to an apparent effect of hydrocarbon preservation in the microbial mat ecosystems.     

Field investigation on the toxicity of Alaska North Slope crude oil (ANSC) and dispersed ANSC crude to Gulf killifish, Eastern oyster and white shrimp

A field investigation was conducted on a Louisiana Spartina alterniflora shoreline to evaluate the toxic effects of crude oil (Alaska North Slope crude oil, ANSC) and dispersed oil (ANSC + dispersant Corexit 9,500) on three aquatic species indigenous to the Gulf of Mexico: Fundulus grandis (Gulf killifish), Crassostrea virginica (Eastern oyster), and Litopenaeus setiferus (white shrimp). Results indicated that total hydrocarbons concentration value in oiled treatments decreased rapidly in 3h and were below 1 ppm at 24h after initial treatment. Corexit 9,500 facilitated more ANSC fractions to dissolve and disperse into the water column. L. setiferus showed short-term sensitivity to the ANSC and ANSC + 9,500 at 30 ppm. However, most test organisms (>83%) of each species survived well after 24h exposure to the treatments. Laboratory tests conducted concurrent with the field investigation indicated that concentrations of crude oil higher than 30 ppm were required for any significant toxic effect on the juvenile organisms tested.     

Photocatalytic pre-treatment with food-grade TiO2 increases the bioavailability and bioremediation potential of weathered oil from the Deepwater Horizon oil spill in the Gulf of Mexico

Using the 2010 Deepwater Horizon oil spill in the Gulf of Mexico as an impetus, we explored the potential for TiO₂-mediated photocatalytic reactive oxygen species (ROS) generation to increase the bioavailability (solubility) and biodegradability of weathered oil after a spill. Food grade TiO₂, which is FDA approved for use as food additive in the United States, was tested as a photocatalyst for this novel application. Photocatalytic pre-treatment (0.05 wt.% TiO₂, UV irradiation 18 W m^?2, 350–400 nm) for 24 h in a bench top photoreactor increased the soluble organic carbon content of weathered oil by 60%, and enhanced its subsequent biodegradation (measured as O₂ consumption in a respirometer) by 37%. Photocatalytic pre-treatment was also tested outdoors under sunlight illumination, but no significant increase in solubility or biodegradation was observed after 11 d of exposure. Although sunlight irradiation of food-grade TiO₂ generated ROS (assessed by the degradation of 4-chlorophenol as a probe compound), the efficacy of weathered oil pre-treatment was apparently hindered by sinking of the photocatalysts under quiescent conditions and illumination occlusion by the oil. Overall, results indicate that photocatalytic pre-treatment to stimulate bioremediation of weathered oil deserves further consideration, but controlling the buoyancy and surface hydrophobicity of the photocatalysts will be important for future efforts to enable ROS generation in proximity to the target compounds.     

Potential biomarkers of crude oil exposure in the gastropod mollusc,Austrocochlea porcata: laboratory and manipulative field studies

Surveys conducted after a crude oil spill indicated that the intertidal gastropod mollusc Austrocochlea porcata may be highly sensitive to the pollutant, and therefore also valuable as a biomonitoring organism. Toxicity tests conducted in the laboratory and field established cause-effect for A. porcata mortalities on exposure to environmentally relevant concentrations of crude oil constituents. Glutathione antioxidant system components (glutathione and glutathione peroxidase, GPx) and oxidative damage (lipid peroxidation) in A. porcata were measured to determine whether any of these biochemical parameters showed potential as biomarkers of sublethal oil exposure. GPx was the most promising candidate for field-based biomarker studies after showing a dose-dependent induction to a crude oil water accommodated fraction (WAF) in laboratory assays. However, subsequent manipulative field experimentation indicated that the GPx response was not sufficiently sensitive and not necessarily predictive of population level effects when measured in situ.     

Role of cyanobacteria in the biodegradation of crude oil by a tropical cyanobacterial mat

Cyanobacterial mats are ubiquitous in tropical petroleum-polluted environments. They form a high biodiversity microbial consortium that contains efficient hydrocarbons degraders. A cyanobacterial mat collected from a petroleum-contaminated environment located in Indonesia was studied for its biodegradation potential. In the field, the natural mat was shown to degrade efficiently the crude oil present in the environment. This natural mat demonstrated also a strong activity of degradation on model crude oil under laboratory conditions. In axenic cultures, the monospecific cyanobacterium Phormidium animale that constitute the bulk of the biomass did not exhibit any degradative capacity on hydrocarbons in the range of C13-C35 carbon atom number either in autotrophic or heterotrophic conditions. It was concluded that this cyanobacterial strain living on a heavily contaminated site had no direct effect on biodegradation of crude oil, the degradation activity being exclusively achieved by the other microorganisms present in the microbial consortium of the mat.     

Microbial processes in the rhizosphere soil of a heavy metals-contaminated Mediterranean salt marsh: a facilitating role of AM fungi

We investigated the relationship of the zonal pattern followed by the vegetation in a polluted Mediterranean salt marsh, in semiarid south-eastern Spain, with the microbiological and biochemical properties (labile C fractions, oxidoreductases and hydrolases) of the rhizosphere soil of two halophyte species, Arthrocnemum macrostachyum and Sarcocornia fruticosa, and with the degree of arbuscular mycorrhizal (AM) colonisation in their rhizospheres. Levels of plant biomass and cover were inversely related to heavy metal contents and salinity. The concentrations of Fe, Cu, Mn and Pb extracted with DTPA hardly varied among the different zones of the salt marsh. The dehydrogenase and phosphatase activities, the soluble C and water-soluble carbohydrates concentrations and the extent of root colonisation were greater in the salt marsh zones of lower soil salinity and lower metal concentration. Urease and beta-glucosidase activities were not detected in the salt marsh. Plant biomass and cover showed positive relationships with mycorrhizal colonisation (R=0.773, P<0.001; R=0.874, P<0.001, respectively). Mycorrhizal colonisation was negatively correlated with the contents of Pb and Zn in plant tissues. This work supports the view that reduced plant uptake of toxic metals, particularly lead, could be involved in the beneficial effects of AM fungi on plant development in Mediterranean salt marshes contaminated with mining wastes.     

Long-term effects of mercury in a salt marsh: hysteresis in the distribution of vegetation following recovery from contamination

During four decades, the Ria de Aveiro was subjected to the loading of mercury from a chlor-alkali industry, resulting in the deposition of several tons of mercury in the sediments. The present study evaluates the impact of this disturbance and the recovery processes, temporally and spatially, by means of examining the richness of the species of salt marsh plants and mercury concentrations in sediments over the last fifty years. The temporal assessment showed that the mercury loading induced a shift in the species composition of the salt marsh from a non-disturbed salt marsh with higher species richness to an alternative state dominated by Phragmites australis. The horizontal assessment, through a mercury gradient, presents the same trend, indicating that P. australis is the species most tolerant to higher mercury concentrations, comparative to Halimione portulacoides, Arthrocnemum fruticosum, Triglochin maritima, Juncus maritimus and Scirpus maritimus. After the reduction of mercury discharges in 1994, the salt marsh shows a slowly return path recovery response. The hysteresis in the response results in the temporal gap between the reduction in mercury concentrations in the sediment and the salt marsh species richness response, comparatively to the existing diversity in the local reference marsh.     

Carbon and nitrogen composition and stable isotope as potential indicators of source and fate of organic matter in the salt marsh of the Changjiang Estuary, China

Elemental (TOC, TN, C/N) and stable carbon and nitrogen isotopic (delta(13)C, delta(15)N) compositions were measured for surface sediments, three sediment vibrocores, plants, and suspended particulate matter (SPM) collected from salt marsh of the Changjiang Estuary. The purpose of this study is to characterize the sources of organic matter in sediments and to further elucidate the factors influencing the isotope signature in the salt marsh. Our results indicate that organic matter preserved in the sediments is predominantly controlled by the particulate organic matter in the Changjiang Estuary. The in situ contribution of marsh plants carbon to sediment organic matter is clearest in the high marsh, where the low delta(13)C of the plants (-28.1 per thousand) is reflected by a sediment delta(13)C (-24.7 per thousand) lower than values found for the low marsh and bare flat sediments (-23.4 per thousand and -23.0 per thousand, respectively). The effect of grain size on the spatial difference of isotope composition in the marsh sediments is insignificant, based on the observation that similar isotope values are found in different size particles, both for delta(13)C and delta(15)N. Nutrient utilization by plant assimilation, however, shows great impact on the surface sediment delta(15)N composition, due to the isotope fractionation. With extensive plant coverage and the consequent low surface water nitrate concentration, delta(15)N values of the high marsh surface sediments show (15)N enrichment.     

Diurnal and seasonal trends in carbonyl levels in a semi-urban coastal site in the Gulf of Campeche,Mexico

Concentrations of formaldehyde, acetaldehyde, acetone, propionaldehyde and butyraldehyde were measured in a semi-urban coastal site in the Gulf of Campeche, Mexico, during the winter, summer and autumn seasons. Measurements were carried out from 10 February 2004 to 16 November 2004. Carbonyl compound levels showed pronounced diurnal and seasonal variations. Maximum concentrations occurred between 13:00 h and 16:00 h, when vehicular traffic and photochemical activity were intense, and during the summer (when there was greater solar radiation). Only acetone during the first campaign (winter) did not correlate with temperature; it showed an inverse diurnal pattern, with higher concentrations during the night, probably due to a local and temporal source. The low concentrations of the main carbonyls found in this study, compared with the values reported for other urban areas, seem to indicate that air quality is still satisfactory in Carmen City.     

Phytoremediation in the tropics--influence of heavy crude oil on root morphological characteristics of graminoids

When studying species for phytoremediation of petroleum-contaminated soils, one of the main traits is the root zone where enhanced petroleum degradation takes place. Root morphological characteristics of three tropical graminoids were studied. Specific root length (SRL), surface area, volume and average root diameter (ARD) of plants grown in crude oil-contaminated and uncontaminated soil were compared. Brachiaria brizantha and Cyperus aggregatus showed coarser roots in polluted soil compared to the control as expressed in an increased ARD. B. brizantha had a significantly larger specific root surface area in contaminated soil. Additionally, a shift of SRL and surface area per diameter class towards higher diameters was found. Oil contamination also caused a significantly smaller SRL and surface area in the finest diameter class of C. aggregatus. The root structure of Eleusine indica was not significantly affected by crude oil. Higher specific root surface area was related to higher degradation of petroleum hydrocarbons found in previous studies.     

Seasonal variation of extracellular enzymatic activity (EEA) and its influence on metal speciation in a polluted salt marsh

The influence of salt marsh sediment extracellular enzymatic activity (EEA) on metal fractions and organic matter cycling was evaluated on a seasonal basis, in order to study the relation between organic matter cycles and the associated metal species. Metals in the rhizosediment of Halimione portulacoides were fractioned according to the Tessier's scheme and showed a similar pattern regarding the organic-bound fraction, being always high in Autumn, matching the season when organic matter presented higher values. Both organic-bound and residual fractions were always dominant, being the seasonal variations due to interchanges between these two fractions. Phenol oxidase and beta-N-acetylglucosaminidase had higher activities during the Spring and Summer, contrarily to peroxidase which had higher activity during Winter. Protease showed high activities in both Spring and Winter. These different periods of high organic matter hydrolysis caused two periods of organic metal bound decrease. Sulphatase peaks (Spring and Winter) matched the depletion of exchangeable metal forms, probably due to sulphides formation and consequent mobilization. This showed an interaction between several microbial activities affecting metal speciation.     

Influence of Spartina alterniflora on the mobility of heavy metals in salt marsh sediments of the Yangtze River Estuary, China

Using bio-disturbed sulphide to trace the mobility and transformation of Cu, Pb, Ni and Zn in the sediments of the Spartina alterniflora-dominated salt marsh in the Yangtze River Estuary, measurements were made of the seasonal variations of acid-volatile sulphide (AVS) and of the simultaneously extracted metals (SEM) in the rhizosphere sediments. Microcosm incubation experiments recreating flooding conditions were conducted to evaluate the effect of AVS and other metal binding phases upon the dynamics of Cu, Pb, Ni and Zn in the salt marsh sediments. The results demonstrate that the ratio values of SEM/AVS have a significant seasonal variation in the rhizosphere sediments and that the anoxic conditions in the sediments were likely enhanced by S. alterniflora during the summer and autumn compared with the anoxic conditions resulting from the native species Phragmites australis and Scirpus mariqueter. The incubation experiments suggest that Fe(III) and Mn(IV/III) (hydr)oxides provide important binding sites for heavy metals under oxic conditions, and sulphide provides important binding sites for the Cu and Pb under anoxic conditions. Our observations indicate that the mobility of heavy metals in the salt marsh sediments is strongly influenced by biogeochemical redox processes and that the invasive S. alterniflora may increase the seasonal fluctuation in heavy metal bioavailability in the salt marsh ecosystem.     

Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

High resolution direct-push profiling over short vertical distances was used to investigate CH(4) attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH(4) and CO(2), and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in δ(13)C(CH4) from an average of -57.6‰ (±1.7‰) in the methanogenic zone to -39.6‰ (±8.7‰) at 105m downgradient, strongly suggest CH(4) attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5m below the water table suggesting that transport of O(2) across the water table is leading to aerobic degradation of CH(4) at this interface. Dissolved N(2) concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O(2) through aerobic degradation of CH(4) or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O(2) rich recharge water were important O(2) transport mechanisms.