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.     

Comparing sediment quality in Spanish littoral areas affected by acute (Prestige, 2002) and chronic (Bay of Algeciras) oil spills

The quality of sediments collected from two areas of the Spanish coast affected by different sources of contaminants has been compared in this study. The areas studied are the coast of Galicia affected by the oil spill from the tanker Prestige (November 2002) and the Gulf of Cádiz which suffers continuous inputs of contaminants from industries located in the area and from oil spills. Contamination by several chemicals (metals, PCBs and PAHs) that bind to sediments was analyzed, and two toxicity tests (Microtox) and amphipod 10-day bioassay) were conducted. PAHs were identified as the compounds responsible for the toxic effects. Results show differences between an acute impact related to the sinking of the tanker Prestige and the chronic impact associated with continuous oil spills associated with the maritime and industrial activities in the Bay of Algeciras, this being the most polluted part of the two coastal areas studied in this work.     

Polynuclear aromatic hydrocarbon contaminants in oysters from the Gulf of Mexico (1986-1990)

Polynuclear aromatic hydrocarbon (PAH) contaminant concentrations in 870 composite oyster samples from coastal and estuarine areas of the Gulf of Mexico analyzed as part of National Oceanographic and Atmospheric Administration's (NOAA's) National Status and Trends (NS&T) Mussel Watch Program exhibit a log-normal distribution. There are two major populations in the data. The cumulative frequency function was used to deconvolute the data distribution into two probability density functions and calculate summary statistics for each population. The first population consists of sites with lower PAH concentration probably due to background contamination (i.e. stormwater runoff, atmospheric deposition). The second population are sites with higher concentrations of PAHs associated with local point sources of PAH input (i.e. small oil spills, etc.). The temporal pattern for the mean concentration of the populations from the Gulf of Mexico is consistent with large-scale climatic factors such as the El Ni?o cycles which affect the precipitation regime.     

不同类型海岸的溢油清理方法

世界石油资源分布和需求的不均衡性,促进了海上石油工业和石油运输业的快速发展,同时也增加了溢油事故的几率.海上溢油污染问题日趋严重,溢油污染对海洋环境、生态、资源、经济及人类生产生活等造成了巨大的影响,日益引起社会各界的关注.海岸溢油污染清理实践表明,正确的溢油清理方案的制定应综合考虑海岸的敏感性指数、溢油的类型、清理方法可能带来的危害以及支际可操作程度等.对包括盐沼地海岸和红树林海岸,沉积海岸,以及岩石海岸三类典型海岸的国内外现有海岸溢油污染清理技术进行了详细的综述,以期为我国的海岸带管理和溢油应急计划的制订提供技术参考.     

Bioremediation process on Brazil shoreline

GOAL, SCOPE AND BACKGROUND: Bioremediation technique can be considered a promising alternative to clean oil spills using microbial processes to reduce the concentration and/or the toxicity of pollutants. To understand the importance of this work we must know that there is only little research performed to date using bioremediation techniques to clean oil spills in tropical countries. So, the main objective of this work is to analyze the behavior of a laboratory's bioremediation test using nutrients on coastal sediments. METHODS: The bioremediation process is followed through geochemical analysis during the tests. This organic material is analyzed by medium pressure liquid chromatography (MPLC), gas chromatography/flame ionization detection (GC/FID) and gas chromatography/ mass spectrometry. By microbial counting, the number of total bacteria and degrading bacteria is determined during the experiments, in order to confirm the effectiveness of the bioremediation process. The seawater obtained throughout the bioremediation process is analyzed for nutrients grade (phosphate and ammonium ions) and also for its toxicity (Microtox tests) due the presence of hydrocarbons and fertilizer. RESULTS: The results from the geochemical analyses of the oil show a relative decrease in the saturated hydrocarbon fraction that is compensated by a relative enrichment on polar compounds. It's confirmed by the fingerprint evaluation where it is possible to see a complete reduction of the normal alkanes followed by isoprenoids. Seawater analysis done by toxicity and nutrients analysis, such as microbial counting (total and degrading bacteria), confirm the fertilizer effectiveness during the bioremediation process. DISCUSSION: Results from simulating test using NPK, a low-price plant fertilizer, suggest that it's able to stimulate the degradation process. Results from medium pressure liquid chromatography (MPLC), done at two different depths (surface and subsurface), show different behavior during the biodegradation process where the later is seen to be more susceptible to microbial attack. Data from bioremediation unit shows a bigger reduction of the saturated fraction, followed by some smaller reduction of aromatic fractions, compensated by a relative increase from polar compounds (NSO). n-C17/pristane, n-C18/ fitane and pristane/fitane rates show constant values for the unity control, different from bioremediation samples which have a significant reduction, especially on subsurface areas, where a strong fall in the rates, seen to be reduced to zero over twenty days, had occurred during the first ten days. However, sample surfaces are reduced to zero in thirty days of experiments, proving that biodegradation is better on subsurfaces. Gaseous chromatography/mass spectrometry (CG/MS) analysis shows constant values to cyclic biomarker rates and aromatic compounds, suggesting that the biodegradation process is not strong enough to reduce these composites. Microbial analysis shows a reduction on heterotrophic (total bacteria) number from control unit, probably because the bacteria uses the spill oil like carbon source and energy. However, the number increases on bioremediation unit, because it uses NPK like a biostimulator. The hydrocarbonoclastic number isn't enough on the first moment, but it's detected after 30 days and quantified in all units, showing big values especially in bioremediation. Toxicity tests confirm that NPK fertilizer does not intoxicate the shoreline during the application of the bioremediation technique. Some nutrient concentration shows high values of ammonium and phosphate per bioremediation unit, reducing by the end of the experiment. CONCLUSIONS: Results reached the goal, finding a proper nutrient (NPK fertilizer) to stimulate the biodegradation process, growing bacteria responsible for reducing impact-contaminated coast ambient by oil spills. Chemical analysis of oil shows a reduction in the saturated fraction with a relative enrichment in polar composites (NSO) and the aromatic fraction from oil remaining constant. Subsurface samples show more biodegradation than surface samples, probably because the first one has higher humidity. Linear alcanes are more biodegraded than isoprenoids, confirming the biodegradation susceptibility order. Saturated cyclic biomarkers and aromatic compounds show constant behavior maybe because the nutrients or time was not enough for microorganismic attack. Fertilizer does not demonstrate any toxic effects in local biota so that it does not compromise the technique applicability and the environment is not saturated by nutrients during the simulation, especially since the coastal environment is an open system affected daily by tides. Therefore, bioremediation tests can be classified as moderate, reaching level 5 in the classification scale by Peters & Moldowan (1993). RECOMMENDATIONS AND PERSPECTIVES: The use of marine environment by the petroleum industry on exploration, production and transportation operation, transform this oil to become the most important pollutant in the oceans. Bioremediation is an important technique used to clean spilled oil impacting on shorelines, accelerating the biodegradation process by using fertilizer growing the microorganisms responsible for decontaminating the environment. We recommend confirming the efficiency of NPK nutrient used on bioremediation simulating experiments on beaches, while monitoring the chemical changes long-term. NPK fertilizer can be used to stimulate the biodegradation process on shoreline impacted by spilled oil.     

Review article: effects of oil pollution, chemically treated oil, and cleaning on thermal balance of birds

The acute effect of oil pollution on birds is on their thermal balance. Oil adheres to the plumage and causes a reduction in water repellant properties of the plumage, causing water to penetrate into the plumage to displace the insulating layer of air. The effect of oil on the plumage insulation is dose-dependent. The effect of oiling is greatly enhanced when the oil is spread in the plumage due to preening. In water, plumage oiling may cause the heat loss to exceed the bird's heat production capacity, resulting in hypothermia. If the oiled bird is ashore, with a dry plumage, it may have a normal thermal insulation. Bird species dependent upon feeding in water (such as diving birds) are therefore much more susceptible to the harmful effects of oil pollution than are semi-aquatic species that can feed ashore. It is possible to restore the water-repelling and insulative properties of the plumage by the process of cleaning if all the oil and soap is removed, and if the plumage is completely dry. Chemical treatment of oil has been suggested as a way to reduce the impact of oil spills on avian life. However, very few reports seem to have addressed the effects of chemically treated oil on the thermal balance of birds, and the results from one study actually indicate that oil treated with dispersants may be more harmful to birds than oil. The urgent need for more information about the effects of chemically treated oil on aquatic birds is therefore stressed.     

Assessment of crude oil biodegradation in arctic seashore sediments: effects of temperature,salinity, and crude oil concentration

The expected increase in offshore oil exploration and production in the Arctic may lead to crude oil spills along arctic shorelines. To evaluate the potential effectiveness of bioremediation to treat such spills, oil spill bioremediation in arctic sediments was simulated in laboratory microcosms containing beach sediments from Barrow (Alaska), spiked with North Slope Crude, and incubated at varying temperatures and salinities. Biodegradation was measured via respiration rates (CO₂ production); volatilization was quantified by gas chromatography/mass spectrophotometry (GC/MS) analysis of hydrocarbons sorbed to activated carbon, and hydrocarbons remaining in the sediment were quantified by GC/flame ionization detector (FID). Higher temperature leads to increased biodegradation by naturally occurring microorganisms, while the release of volatile organic compounds was similar at both temperatures. Increased salinity had a small positive impact on crude oil removal. At higher crude oil dosages, volatilization increased, however CO₂ production did not. While only a small percentage of crude oil was completely biodegraded, a larger percentage was volatilized within 6–9 weeks.     

A Holistic Approach to Hydrocarbon Source Allocation in the Subtidal Sediments of Prince William Sound,Alaska, Embayments

Prince William Sound (PWS), Alaska has an extensive history of human and industrial activity that has produced a complex organic geochemistry record in subtidal sediments of embayments throughout the sound. In addition to contributions from recent oil spills and a regional background of natural petroleum hydrocarbons originating from active hydrocarbon systems in the northern Gulf of Alaska (GOA), pyrogenic and petrogenic PAH were, and continue to be introduced to subtidal sediments at numerous sites of past and present human activities. These sites include villages, fish hatcheries, fish camps and recreational campsites in addition to abandoned settlements, canneries, sawmills, and mines. A holistic approach is used to fingerprint and quantify hydrocarbon contributions from multiple sources in a sediment sample. It involves acquiring a comprehensive understanding of the history of the area to identify potential sources, collection of representative samples, and accurate quantitative analyses of the source and sediment samples for a suite of diagnostic PAH analytes and chemical biomarker compounds. Unlike the deepwater sediments of the sound and GOA, the TOC tool, described elsewhere, does not work as well in some restricted embayments due to their high contents of recent organic matter (ROM). The current study employs a constrained least-squares algorithm to allocate hydrocarbon sources contributing to subtidal sediments collected from PWS embayments in 1991, 1999 and 2000. Results show that sources contributing to the natural petrogenic background are present in the embayments, pyrogenic hydrocarbons including combustion products of diesel are important where human activity was high, and petroleum produced from the Monterey Formation (CA) is present locally. Oil and asphalt shipped from California were widely used for fuel and construction prior to development of the Cook Inlet and North Slope fields. In certain locations that were oiled in 1989, low levels of highly degraded Alaska North Slope crude oil residues attributable to the Exxon Valdez spill remain.     

Econometric modelling, estimation and policy analysis of oil spill processes

This paper explores approaches to model specification suitable for empirical investigation of a stochastic oil spill model. We focus on the effects of economic incentive measures on the frequency of oil spills, spill size, and volume of oil spilled. We look into the relationships between parameters that describe the spill generation process and the enforcement effort, using data for the Black and Baltic Seas.     

Polycyclic aromatic hydrocarbons in fuel-oil contaminated soils, Antarctica

Where fuel oil spills have occurred on Antarctic soils polycyclic aromatic hydrocarbons (PAH) may accumulate. Surface and subsurface soil samples were collected from fuel spill sites up to 30 years old, and from nearby control sites, and analysed for the 16 PAHs on the USEPA priority pollutants list, as well as for two methyl substituted naphthalenes, 1-methylnaphthalene and 2-methylnaphthalene. PAH levels ranged from 41-8105 ng g-1 of dried soil in the samples from contaminated sites and were below detection limits in control site samples. PAH were detected in surface soils and had migrated to lower depths in the contaminated soil. The predominant PAH detected were naphthalene and its methyl derivatives.     

Treatment of oil spill by sorption technique using fatty acid grafted sawdust

Treatment of oil spills remains a challenge to environmental scientists and technologists. Among all the existing techniques used for oil treatment, sorption is a popular technique because it is cheap, simple and effective. Among the various sorbents used, sawdust appears to be the most attractive material in terms of cost, versatility and abundance. In the present work, the efficacy of surface modification of sawdust by fatty acids (oleic acid, stearic acid and decanoic acid) and vegetable oils (castor oil or mustard oil) is demonstrated. Sorption of seawater contaminated with crude oil and also weathered oil was greatly enhanced by the surface modification. The results show that oleic acid grafted sawdust (OGSD) has the best sorption capacity for crude oil as well as weathered oil.     

Multifunctional metal-organic frameworks in oil spills and associated organic pollutant remediation

The release of toxic organic compounds into the environment in an event of oil spillage is a global menace due to the potential impacts on the ecosystem. Several approaches have been employed for oil spills clean-up, with adsorption technique proven to be more promising for the total reclamation of a polluted site. Of the several adsorbents so far reported, adsorbent-based porous materials have gained attention for the reduction/total removal of different compounds in environmental remediation applications. The superior potential of mesoporous materials based on metal–organic frameworks (MOFs) against conventional adsorbents is due to their intriguing and enhanced properties. Therefore, this review presents recent development in MOF composites; methods of preparation; and their practical applications towards remediating oil spill, organic pollutants, and toxic gases in different environmental media, as well as potential materials in the possible deployment in reclaiming the polluted Niger Delta due to unabated oil spillage and gas flaring.

     

Bottom sediments of the Arabian Gulf--II. TPH and TOC contents as indicators of oil pollution and implications for the effect and fate of the Kuwait oil slick

Measurements of total petroleum hydrocarbon (TPH) concentrations in 77 core samples collected in 1992 from the bottom sediments of the Arabian Gulf were used to delineate oil pollution levels and their distribution in the region. Seven chronic moderately (TPH 50-89 microg g(-1)) and heavily (TPH 266-1448 microg g(-1)) polluted areas were identified; three in the northern part of the region and four in the southern part. Oil pollution in these areas was attributed to natural oil seepage, accidental damage to pipelines, accidental spillage from tankers, the Nowruz oil slick, and tanker deballasting. Present-day intermediate (TPH 50-114 microg g(-1)) and high (TPH 200-1122 microg g(-1)) pollution levels were identified in 10 areas. Of these, three polluted areas in the northeastern corner, offshore Saudi Arabia and offshore Bahrain, Qatar and United Arab Emirates are probably directly affected by the Kuwait oil slick. A new scenario is suggested for the movement and fate of the oil slick, in which additional large oil discharges from northern sources, as well as substantial quantities of eroded oiled sediments and oil floating from heavily impacted tidal flats along the Saudi Arabian coastline, serve as sources of oil pollution. A definite relationship exists between the grain-size distribution and the TPH content of bottom sediments, with the highest TPH concentrations in the muddy sediments, suggesting that adsorption onto muds is the primary mechanism of oil pollutant accumulation in the Arabian Gulf. Total organic carbon measurements do not correlate positively with the grain-size distribution and TPH contents of the sediments, and hence cannot be used as indicators for petroleum hydrocarbon pollution in the Arabian Gulf.     

A Holistic Approach to Hydrocarbon Source Allocation in the Subtidal Sediments of Prince William Sound,Alaska, Embayments

Prince William Sound (PWS), Alaska has an extensive history of human and industrial activity that has produced a complex organic geochemistry record in subtidal sediments of embayments throughout the sound. In addition to contributions from recent oil spills and a regional background of natural petroleum hydrocarbons originating from active hydrocarbon systems in the northern Gulf of Alaska (GOA), pyrogenic and petrogenic PAH were, and continue to be introduced to subtidal sediments at numerous sites of past and present human activities. These sites include villages, fish hatcheries, fish camps and recreational campsites in addition to abandoned settlements, canneries, sawmills, and mines. A holistic approach is used to fingerprint and quantify hydrocarbon contributions from multiple sources in a sediment sample. It involves acquiring a comprehensive understanding of the history of the area to identify potential sources, collection of representative samples, and accurate quantitative analyses of the source and sediment samples for a suite of diagnostic PAH analytes and chemical biomarker compounds. Unlike the deepwater sediments of the sound and GOA, the TOC tool, described elsewhere, does not work as well in some restricted embayments due to their high contents of recent organic matter (ROM). The current study employs a constrained least-squares algorithm to allocate hydrocarbon sources contributing to subtidal sediments collected from PWS embayments in 1991, 1999 and 2000. Results show that sources contributing to the natural petrogenic background are present in the embayments, pyrogenic hydrocarbons including combustion products of diesel are important where human activity was high, and petroleum produced from the Monterey Formation (CA) is present locally. Oil and asphalt shipped from California were widely used for fuel and construction prior to development of the Cook Inlet and North Slope fields. In certain locations that were oiled in 1989, low levels of highly degraded Alaska North Slope crude oil residues attributable to the Exxon Valdez spill remain.     

Alkytcyclohexanes in Environmental Geochemistry

The n -alkylated cyclohexanes (CHs) are a homologous series of hydrocarbon compounds that are commonly present in crude oil and refinery products such as diesel fuel. These compounds exhibit specific distribution patterns for different fuel types, providing useful fingerprints for characterizing petroleum products, especially after degradation of n -alkanes has occurred. However, there are no published data to show how these compounds are altered in the environment after long-term spillage of petroleum products. This paper presents two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation. These spills are the 1979 crude-oil spill in Bemidji, Minnesota, and a chronic diesel-fuel spillage from 1953-1991 at Mandan, North Dakota. The alkyl CHs in both spilled oil products are affected by similar biodegradative processes in which the compounds undergo a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation results in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. This pattern is the opposite of low-end loss expected with weathering and aerobic biodegradation. The enhancement of the low molecular mass alkyl CH homologs, if not recognized as a degradative pathway of diesel fuel in an anaerobic environment, can potentially be misinterpreted in fuel-oil fingerprinting as deriving from lower distillation-range fuels or admixture of diesel with other fuels.     

Alkylcyclohexanes in Environmental Geochemistry

The n -alkylated cyclohexanes (CHs) are a homologous series of hydrocarbon compounds that are commonly present in crude oil and refinery products such as diesel fuel. These compounds exhibit specific distribution patterns for different fuel types, providing useful fingerprints for characterizing petroleum products, especially after degradation of n -alkanes has occurred. However, there are no published data to show how these compounds are altered in the environment after long-term spillage of petroleum products. This paper presents two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation. These spills are the 1979 crude-oil spill in Bemidji, Minnesota, and a chronic diesel-fuel spillage from 1953–1991 at Mandan, North Dakota. The alkyl CHs in both spilled oil products are affected by similar biodegradative processes in which the compounds undergo a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation results in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. This pattern is the opposite of low-end loss expected with weathering and aerobic biodegradation. The enhancement of the low molecular mass alkyl CH homologs, if not recognized as a degradative pathway of diesel fuel in an anaerobic environment, can potentially be misinterpreted in fuel-oil fingerprinting as deriving from lower distillation-range fuels or admixture of diesel with other fuels. Published by Elsevier Science Ltd on behalf of AEHS.     

Investigation of evaporation and biodegradation of fuel spills in Antarctica: II-extent of natural attenuation at Casey Station

In many temperate regions, fuel and oil spills are sometimes managed simply by allowing natural degradation to occur, while monitoring soils and groundwater to ensure that there is no off-site migration or on-site impact. To critically assess whether this approach is suitable for coastal Antarctic sites, we investigated the extent of evaporation and biodegradation at three old fuel spills at Casey Station. Where the contaminants migrated across frozen ground, probably beneath snow, approximately half the fuel evaporated in the first few months prior to infiltration at the beginning of summer. Once in the ground, however, evaporation rates were negligible. In contrast, minor spills from fuel drums buried in an abandoned waste disposal site did not evaporate to the same extent. Biodegradation within all three spill sites is generally very minor. We conclude that natural attenuation is not a suitable management strategy for fuel-contaminated soils in Antarctic coastal regions.     

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.     

Permanent seafloor anoxia in coastal basins of the northwestern Gulf of Finland, Baltic Sea

The Gulf of Finland is regularly affected by inflows of anoxic deep-water masses from the northern Baltic proper. These dense water masses advance over large areas with a decline of benthic life in affected areas as a result. Such events have been regularly repeated over decades and centuries. The archipelago, however, is well protected, because the inflows of anoxic deep waters do not enter such shallow waters. The situation could thus be better for benthic life in the archipelago, but in many areas this is not true. In areas where the bottoms are sheltered from storms and currents, permanent anoxia can persist for decades. Such areas were found in the western archipelago of the Gulf of Finland. Examination of surface cores revealed that many of these basins have been continuously anoxic for almost 40 years. A deeper coring showed that, at least locally, shallow water seafloor anoxia has been a fact in the area for thousands of years.     

Oil Identification Based on a Goodness-of-Fit Metric Applied to Hydrocarbon Analysis Results

Assessment of environmental damage following accidental oil spills requires reliable oil identification methods. Results from hydrocarbon analyses of environmental samples are often difficult to interpret, because of the changes in oil composition (or weathering) that follows release into the environment, and because of confounding by hydrocarbons from other sources. To a first-order approximation, weathering proceeds according to simple first-order loss-rate (FOLR) kinetics for polycyclic aromatic hydrocarbons (PAH) based on molecular size. This relationship between relative weathering rate and molecular size can be exploited to infer the initial PAH composition of spilled oils, and this information can be combined with results for weathering-invariant analytes to substantially increase the precision and accuracy of hydrocarbon source recognition methods. The approach presented here evaluates a goodness-of-fit metric between the measured hydrocarbon composition of an environmental sample and a suspected source, after correcting for PAH weathering losses based on FOLR kinetics. Variability from analytical and sampling error may thus be accounted for, and source identifications can be expressed as objective probability statements. This approach is illustrated by application to four independent case studies.