Long-term chemical effects of petroleum in south Louisiana wetlands—I. Organic carbon in sediments and waters

The chemical effects of chronic petroleum input into a shallow water marsh were examined by measuring hydrocarbon levels and dissolved organic carbon content of sediments associated with two active oil fields in south Louisiana. Annual levels of total organic carbon in the surface waters of the oil fields were higher by 1 mg C/l. in the salt marsh and 5 mg C/l. in the fresh marsh than the respective controlsites. Average dissolved organic carbon concentrations in the interstitial waters of cores taken within the oil field environments were 105% higher than the control in the salt marsh and 43% higher than the control in the fresh marsh. Significantly lower ratios of C₁₇ to pristane occurred in both oil field sediments; however, average odd-even predominance values were not indicative of petroleum contaminated sediments. The results indicate that microbial processes are responsible for dissolution of petroleum into dissolved organic carbon and that dissolved organic carbon concentrations may be a more significant measure of chronic petroleum input than hydrocarbon distribution.     

Gladstone, Australia Field Studies: Weathering and Degradation of Hydrocarbons in Oiled Mangrove and Salt Marsh Sediments With and Without the Application of an Experimental Bioremediation Protocol

This field study was a combined chemical and biological investigation of the relative rates of weathering and biodegradation of oil spilled in sediments and testing the influence of a bioremediation protocol. The aim of the chemistry work presented here was to determine whether the bioremediation protocol affected the rate of penetration, dissipation or long-term retention of a medium range crude oil (Gippsland) and a Bunker C oil stranded in tropical Rhizophora sp. mangrove and Halosarcia sp. salt marsh environments. Permission for the planned oil spills was granted in the Port Authority area of Gladstone, Queensland (Australia). Sediment cores from three replicate plots of each treatment for mangroves and four replicate plots for the salt marsh (oil only and oil plus bioremediation) were analysed for total hydrocarbons (THC) and for individual alkane markers using gas chromatography with flame ionization detection (GC–FID). Sediments were collected at day 2, then 1, 2, 5 or 6 and 12 or 13 months post-spill for mangroves and day 2, 1, 3 and 9 months post-spill for salt marshes. Over this time, hydrocarbons in all of the oil treated plots decreased exponentially. There was no statistical difference in initial oil concentrations, penetration of oil to depth, or in the rates of oil dissipation between untreated oil and bioremediated oil in the mangrove plots. The salt marsh plots treated with the waxy Gippsland oil showed a faster rate of biodegradation of the oil in the bioremediated plots. In this case only, the degradation rate significantly impacted the mass balance of remaining oil. The Bunker C oil contained only minor amounts of highly degradable n-alkanes and bioremediation did not significantly impact its rate of loss in the salt marsh sediments. At the end of each experiment, there were still n-alkanes visible in the gas chromatograms of residual oils. Thus it was concluded that there was unlikely to be any change in the stable internal biomarkers of the oils over this time period. The predominant removal processes in both habitats were evaporation and dissolution, with a lag-phase of 1–2 months before the start of microbial degradation.     

Hydrocarbon contamination on the Antarctic peninsula: III. The Bahia Paraiso—Two years after the spill

Two years after the release of 600 000 l of diesel fuel arctic into Arthur Harbor, little spill-related contamination can be detected in intertidal limpets (Nacella concinna) and subtidal sediments. Periodic releases of small amounts of material from the ship oil nearby islands, in particular the intertidal areas of Christine, Limitrophe and Humble Islands. Subtidal sediment contamination is primarily due to other local inputs such as ship, boating and station activities. Beaches were unusually contaminated after 2 yr, but quiescent weather conditions, occasional releases from the wreck, and prevailing currents may concentrate hydrocarbon contamination in relatively low energy areas. Intertidal limpets (N. concinna) collected along these beaches were also contaminated. The volatility of the fluid, the amount spilled, and the dynamic weather and current conditions in Arthur Harbor tended to minimize long-term contamination of the area.     

The West Falmouth oil spill after 20 years: Fate of fuel oil compounds and effects on animals

The barge Florida spilled No. 2 fuel oil into Buzzards Bay, Massachusetts on 29 September 1969. Sediments from five of the original stations were sampled in August 1989 and analysed for fuel oil hydrocarbons. Two subtidal and one intertidal marsh station showed no evidence of fuel oil. One subtidal mud core had traces of biodegraded fuel oil at 10–15 cm. One marsh core contained 10⁻⁶ g g⁻¹ dry wt of weathered and biodegraded fuel oil aromatic hydrocarbons and cycloalkanes at 5–10 cm with lesser concentrations at 0–5 and 10–15 cm. Although present in trace concentrations, these hydrocarbons appear to be slightly inducing cytochrome P4501A in marsh fish (Fundulus heteroclitus).     

Consequences of linseed oil spills in salt marsh sediments

In a simulated spill in a salt marsh, linseed oil penetrated rapidly into the sediments at a rate of 10(-7) cm2 s(-1). The oil concentration remained unchanged for the first month after the spill, but 60% of the oil disappeared from the top 30 cm after a further month. The oil adsorbed to and accumulated in the muddy sediments (top 15 cm) leading to decreased sediment permeability, pH, Eh, abundance of plant roots and infauna and to the establishment of anoxic conditions. These changes accompanied transformations in the original fatty acid composition of the linseed oil, mainly associated with a decrease in 18 : 3omega3, an increase in the other fatty acids and the presence of 'new' fatty acids. A rapid increase in the abundance of heterotrophic aerobic and anaerobic bacteria and aerobic oil degrading bacteria, suggested that these micro-organisms degraded the oil. The role of the bacteria in oil degradation was confirmed in laboratory experiments where the fatty acids composition of the linseed oil underwent identical transformations to those obtained in the field. The degradation of linseed oil appears to be a sequential process initiated by aerobic and/or anaerobic bacteria and continued by sulphate reducing bacteria, which were unable to degrade the raw oil.     

The 1974 spill of the Bouchard 65 oil barge: petroleum hydrocarbons persist in Winsor Cove salt marsh sediments

Petroleum hydrocarbons persist in salt marsh sediments in Winsor Cove (Buzzards Bay, Massachusetts) impacted from the 1974 spill of No. 2 fuel oil by the barge Bouchard 65. Intertidal sediment cores were collected from 2001 to 2005 and analyzed for total petroleum hydrocarbons (TPHs). TPHs content was greatest (as high as 8.7 mg g(-1) dry weight) in the surface sediments and decreased with distance landward. Select samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) with values as high as 16.7 microg g(-1) for total naphthalenes and phenanthrenes/anthracenes. These remaining PAHs are mainly C(4)-naphthalenes and C(1)-, C(2)-, and C(3)-phenanthrenes/anthracenes revealing preferential loss of almost all of the naphthalenes and the parent compound phenanthrene. Inspection of the data indicates that biodegradation, water-washing and evaporation were major removal processes for many of the petroleum hydrocarbons in the marsh sediments. In addition, historical data and photographs combined with their recent counterparts indicate that erosion has physically removed these contaminants from this site.     

Subgrid modeling of salt marsh hydrodynamics with effects of vegetation and vegetation zonation

Vegetation plays a critical role in modifying inundation and flow patterns in salt marshes. In this study, the effects of vegetation are derived and implemented in a high‐resolution, subgrid model recently developed for simulating salt marsh hydrodynamics. Vegetation‐induced drag forces are taken into account as momentum sink terms. The model is then applied to simulate the flooding and draining processes in a meso‐tidal salt marsh, both with and without vegetation effects. Marsh inundation and flow patterns are significantly changed with the presence of vegetation. A smaller area of inundation occurs when vegetation is considered. Tides propagate both on the platform and through the channels when vegetation is absent, whereas flows concentrate mainly in channels when vegetation is present. Local inundation on vegetated platforms is caused mainly by water flux spilled from nearby channels, with a flow direction perpendicular to the channel edges, whereas inundation on bare platforms has contributions from both local spilled‐over water flux and remote advection from adjacent platforms. The flooding characteristics predicted by the model showed a significant difference between higher marsh and lower marsh, which is consistent with the wetlands classification by the National Wetlands Inventory (NWI). The flooding characteristics and spatial distribution of hydroperiod are also highly correlated with the vegetation zonation patterns observed in Google Earth imagery. Regarding the strong interaction between flow, vegetation and geomorphology, the conclusion highlights the importance of including vegetation in the modeling of salt marsh dynamics. Copyright © 2017 John Wiley & Sons, Ltd.     

Seasonal changes in surface level of a salt marsh creek

Nineteen surveys were carried out over a two-year period to determine the surface height of a salt marsh creek located on the north side of the River Esk, Cumbria, England. An AGA 112 electromagnetic distance measurer mounted on a Wild TI theodolite was used in conjunction with acrylic reflectors to follow the form of the ground. The results showed that there were no significant net trends in surface level, although seasonal variations of the order of 2 cm occurred. Vegetated areas responded in similar fashion to bare surfaces. It is thought that the elevational changes were attributable to the swelling of clay particles during the winter months rather than the effects of erosion and accretion.     

Transport of mecoprop from agricultural soils to an adjacent salt marsh

Salt marshes are important ecological areas and play a significant role in coastal flood defence schemes. In many areas of the UK they are adjacent to agricultural areas utilised for the growth of cereal crops, for which mecoprop is used as a selective herbicide in the control of broad-leaf weeds. This study measured concentrations of mecoprop in soils, drainage ditch waters and sediments and salt marsh sediments over a period of 138 days following spring application. Soil concentrations of up to 1827 microg/g were recorded after application, which demonstrated a half life for mecoprop of from 9 to 12 days, with first order kinetics. However, a major rainfall event 9 days after application resulted in significant transport of herbicide to the salt marsh via subsurface field drains, drainage ditches and discharge sluice. Mecoprop concentrations of up to 386 microg/l observed in water samples were above UK guidelines.     

The Eleni V oil spill: Return to normal conditions

The fate and effects of Eleni V oil spilled in May 1978 have been followed until May 1980. At a mechanically-cleaned and exposed beach the hydrocarbon concentrations of inshore water and mussel tissue returned to background values between 300 and 400 days after the beaches became visually clean. Oil remaining on the surface of a protected beach still showed little degradation compared to oil buried in a disposal pit. Even on mobile beaches subject to high wave-energy, mechanical retrieval and clean-up of such a persistent heavy fuel oil is considered necessary unless its redistribution by wave action over adjoining beaches and into sediments is considered acceptable.     

The mobility, partitioning and degradation of atrazine and simazine in the salt marsh environment

The transfer of the s-triazine herbicides onto a salt marsh and their subsequent behaviour and fate has been investigated in a series of laboratory-based experiments. The results indicate that atrazine and simazine enter the marsh system and undergo negligible adsorption onto suspended solids. Herbicide accumulation within the sediment compartment was thought to be due to other mechanisms such as partitioning into the surface microlayer, or association with sediment flocs. s-Triazine mobility within the sediment was dictated by compound and sediment type, reflecting greater mobility in the mud flat than the vegetated marsh sediment. The majority of the herbicides were, however, retained in the uppermost layers of the sediment profile indicating that salt marsh sediments act as a sink for these compounds. Although degradation rates in the sediment were relatively rapid, detectable levels of the parent compounds were still evident after 71 days, which implies that these compounds may persist in salt marsh sediments. The absence of degradation in the aqueous phase implies that adsorption to particulate matter is a prerequisite for the degradation of the s-triazine herbicides.     

GEOCHEMICAL RECOGNITION OF SPILLED SEDIMENTS USED IN NUMERICAL MODEL VALIDATION

A fixed link (tunnel and bridge, in total 16 km) was constructed between Sweden and Denmark during 1995-2000. As part of the work, approximately 16 million tonnes of seabed materials (limestone and clay till) were dredged, and about 0.6 million tonnes of these were spilled in the water. Modelling of the spreading and sedimentation of the spilled sediments took place as part of the environmental monitoring of the construction activities. In order to verify the results of the numerical modelling of sediment spreading and sedimentation, a new method with the purpose of distinguishing between the spilled sediments and the naturally occurring sediments was developed. Because the spilled sediments tend to accumulate at the seabed in areas with natural sediments of the same size, it is difficult to separate these based purely on the physical properties. The new method is based on the geo-chemical differences between the natural sediment in the area and the spill. The basic propertiesused are the higher content of calcium carbonate material in the spill as compared to the natural sediments and the higher Ca/Sr ratio in the spill compared to shell fragments dominating the natural calcium carbonate deposition in the area. The reason for these differences is that carbonate derived from recent shell debris can be discriminated from Danien limestone, which is the material in which the majority of the dredging took place, on the basis of the Ca/Sr ratio being 488 in Danien Limestone and 237 in shell debris. The geochemical recognition of the origin of the sediments proved useful in separating the spilled from the naturally occurring sediments. Without this separation, validation of the modelling of accumulation of spilled sediments would not have been possible. The method has general validity and can be used in many situations where the origin of a given sediment is sought.     

Americium in intertidal sediments from the coastal environs of Windscale

The distribution of americium in surface intertidal sediments from a coastal environment near the Windscale nuclear fuel reprocessing plant has been investigated. The study includes data on the broadscale distribution of ²⁴¹Am in Northwest England, but focuses on the sediments of the Ravenglass estuary 10 km south of Windscale. The results indicate that americium concentrations in the inner estuary sediments are up to seven times higher than those from the Irish Sea itself. Americium distribution on silt banks is rather constant on a small scale, but varies considerably between adjacent silt bank and salt marsh areas.     

Trace metals in estuarine sediments from the southwestern Spanish coast

The impact of river-transported metal pollution and industrial wastes on the metal distribution (Cr, Cu, Zn, Pb) in estuarine sediments was studied in the southwestern Spanish estuaries. Intertidal and subtidal surface sediments of the Tinto-Odiel Estuary are very highly polluted by heavy metals, with geoaccumulation indices up to 4 in the three sedimentary environments studied (channel, channel border and salt marsh). The single exception is the Punta Umbria channel, very protected from the point sources by salt marsh deposits and hydraulic processes. In the remaining two estuaries, pollution (Pb, Cu) was only significant near the harbour situated in the Piedras river mouth, whereas very low values were found in the Guadiana Estuary. In these last rivers, the enrichment factor increases from the channel to the salt marsh sediments.     

Recovery of interior brackish marshes seven years after the chalk point oil spill

Seven years after the April 2000 spill of 140,000 gallons of a mixture of No. 6 and No. 2 fuel oils in the Patuxent River, Maryland, heavily oiled brackish marshes showed continuing effects. Stem density and stem height were significantly lower in oiled versus unoiled sites for Spartina alterniflora but not Spartina cynosuroides habitats. In contrast, belowground biomass was significantly lower in S. cynosuroides habitats but not S. alterniflora habitats. Total PAH concentrations were up to 453 mg/kg in surficial soils (0-10 cm) and 2921 mg/kg with depth (10-20 cm). The oil had lost 22-76% of its initial PAH content after seven years, although the oil in marsh soils has undergone little to no additional weathering since Fall 2000. Based on amphipod acute toxicity tests and sediment quality guidelines, 25% of the soils in the marsh are expected to be toxic (ESB-TU_FCV values > 3.0; P_Max > 0.65).     

Agricultural inputs of mecoprop to a salt marsh system: Its fate and distribution within the sediment profile

The mass of mecoprop discharged in agricultural drainage waters directly onto a salt marsh has been determined and the subsequent fate and distribution of mecoprop within the vegetated and mud flat sediments investigated. The results show the leaching of high mecoprop concentrations from the agricultural soils following heavy rain, with peak concentrations in drainage waters preceding peak water discharges. A direct increase in mecoprop concentration within salt marsh sediments was also identified and, consequently, a preliminary evaluation of the potential threat of the mecoprop loadings to the indigenous biota of the dynamic salt marsh system was made.     

Are sea otters being exposed to subsurface intertidal oil residues from the Exxon Valdez oil spill?

Twenty years after the Exxon Valdez oil spill, scattered patches of subsurface oil residues (SSOR) can still be found in intertidal sediments at a small number of shoreline locations in Prince William Sound, Alaska. Some scientists hypothesize that sea otters continue to be exposed to SSOR by direct contact when otters dig pits in search of clams. This hypothesis is examined through site-specific examinations where SSOR and otter-dug pits co-occur. Surveys documented the exact sediment characteristics and locations on the shore at the only three subdivisions where both SSOR and otter pits were found after 2000. Shoreline characteristics and tidal heights where SSOR have persisted are not suitable habitat for sea otters to dig pits during foraging. There is clear separation between areas containing SSOR and otter foraging pits. The evidence allows us to reject the hypothesis that sea otters encounter and are being exposed by direct contact to SSOR.     

Contribution of primary producers to mercury trophic transfer in estuarine ecosystems: Possible effects of eutrophication

There is an ongoing eutrophication process in the Ria de Aveiro coastal lagoon (Portugal), with progressive replacement of rooted primary producers for macroalgae. Taking advantage of a well-defined environmental contamination gradient, we studied mercury accumulation and distribution in the aboveground and the belowground biomass of several salt marsh plants, including the seagrass species Zostera noltii and the dominant green macroalgal species Enteromorpha sp. The results of these experiments were then placed into the context of the estuarine mercury cycle and transport from the contaminated area.All salt marsh plants accumulated mercury in the root system, with Halimione portulacoides showing the highest levels, with up to 1.3 mg kg⁻¹ observed in the most contaminated area. Belowground/aboveground ratios were generally below 0.4, suggesting that salt marsh plants are efficient immobilizers and retainers of mercury agents. Moreover, due to their sediment accretion capacities, salt marsh plants seem to play an important role in the sequestration of mercury in estuarine sediments.Seagrasses, on the other hand, accumulated considerable amounts of mercury in the aboveground biomass with belowground/aboveground ratios reaching as high as 1.4. These results may be due to their different routes of uptake (roots and foliar uptake) which suggests that seagrass meadows can be an important agent in the export of mercury from contaminated areas, considering the high aboveground biomass replacement rates.Rooted macrophytes accumulate less mercury in their aboveground biomass than macroalgae. The change of primary producer dominance due to eutrophication can originate a 4- to 5-fold increase in primary producer associated mercury. This mercury would be available for export, making it bioavailable to estuarine food webs, which stresses the need to reverse the current eutrophic status of estuarine systems.     

The dose-response relationship between No. 2 fuel oil and the growth of the salt marsh grass,Spartina alterniflora

The effect of No. 2 fuel oil on the biomass production of the salt marsh plant, Spartina alterniflora, was studied in a greenhouse dose-response experiment. S. alterniflora were transplanted into soil with 10 dosage levels of No. 2 fuel oil ranging from 0 to 456 mg g(-1) dry soil. Three months after transplantation, values for plant biomass, stem density, and shoot height decreased significantly with increasing fuel oil level in a dose-response fashion. Evapo-transpiration rates were correlated with the total biomass response. Relative to the control, a significant decrease in total (above- plus below-ground) plant biomass was observed at concentrations above 57 mg g(-1) dry soil. Within the 3-month experimental period, detrimental effects on below-ground biomass accumulation and bioluminescence of the marine bacterium Viberio fisheri in the Microtox Solid Phase Test were observed at oil concentrations >29 mg g(-1) dry soil, suggesting that biological effects of oil within the sediment matrix may be more pronounced than on above-ground biomass, requiring a dosage 228 mg g(-1) dry soil to elicit a significant detrimental effect. Hence, measurements of oil effects with biological end-points based solely on above-ground responses may underestimate the potential impacts of petroleum hydrocarbon spills, especially when the oil has penetrated the soil. While S. alterniflora was proved to be relatively tolerant to the No. 2 fuel oil spills, its effectiveness in phytoremediation operations may be limited at fuel oil levels 228 mg g(-1) dry soil, as both plant growth and microbial activity may be constrained.     

Size-selective mortalities of clams in an oil spill site

Mixed No. 2 fuel oil and JP5 jet fuel, following an oil spill into Long Cove, Searsport, Maine, U.S.A., in March 1971 became concentrated locally at levels up to more than 250 ppm in intertidal sediments from 15 to 25 cm below the surface and continued until 1976 to kill successive year class juvenile clams as in normal growth behaviour they burrowed down through redistributed overlying clean sediments into the oil concentration beneath.