Brazilian Oil Spills Chemical Characterization--Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds--benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Brazilian Oil Spills Chemical Characterization—Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds—benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Microplastics in aquatic environment: characterization,ecotoxicological effect,implications for ecosystems and developments in South Africa

Microplastics are small-size plastic piece scales (particles <?5 mm) in sediments and waters which interact with environment and organisms by various means. Microplastics are becoming a universal ecological concern since they may be a source of hazardous chemicals to marine organisms and environments. Recent research suggests microplastics could enable the transfer of hydrophobic aquatic pollutants or chemical additives to biota. Even though microplastic presence and interactions are recently being detected in marine and freshwater systems, the fate of microplastics is still very poorly understood. This literature review is a summary of the sources and transport of microplastics, their interactions with toxic chemicals and the methodologies for chemical quantification and characterization of microplastics. The environmental outcome and impact of microplastics in wastewater treatment plants were assessed as well as the trends and update on microplastic research in the South African aquatic ecosystem.

     

Determination of PAH sources in dated sediments from Green Bay, Wisconsin, by a chemical mass balance model

Six sediment cores were collected from Green Bay, Wisconsin, in order to identify possible sources of polycyclic aromatic hydrocarbons (PAHs) by a chemical mass balance (CMB) model. The cores which were obtained in 1995 had total PAH concentrations between 8.04 and 0.460 ppm. 210Pb and 137Cs dating was used to determine historical trends of PAH inputs, and elemental carbon particle analysis was done to characterize particles from combustion of coal, wood and petroleum. The results show that coke burning, highway dust, and wood burning are likely sources of PAHs to Green Bay. The contribution of coke oven emissions (CB) for the Green Bay cores is in the range of 5 to 90%. The overall highway dust (HWY) contribution is between 5 and 70%. There is a maximum (approximately 67%) contribution of HWY around 1988 which is in agreement with the historical US petroleum consumption. The wood burning (WB) contribution is between 1 to 30%, except in core GB-A where a maximum (approximately 50%) is found around 1994. The average relative errors of measurement for x2 equal to the number of degrees of freedom, are 52.5, 56.2, 36.2, 52.3, and 42.8 (df = 3) for the Green Bay cores A, B, C, E, and F, respectively. The sums of the contribution factors are less than one, indicating gain of inert biological or other bulk material between source and receptor. The results of carbon particles for Green Bay core D show that coal, oil, and wood burning are consistent with the CMB modeling results.     

Determination of the applicability of CERCLA's petroleum exclusion at contaminated sites – focus on metals

Areas impacted by petroleum refining and handling operations may become subject to CERCLA enforcement. Because of CERCLA's petroleum exclusion clause, determining whether contamination in a CERCLA Site originated from petroleum products or hazardous wastes becomes important. Because certain metals are typically enriched in wastes relative to petroleum products and background soils, knowledge of metal contents in these potential end member metal sources is an important step towards contaminant source identification in soils and sediments. In LNAPL plumes, metal content, particularly lead, may be claimed to be the result of wastes mishandling and not due only to the presence of leaded gasoline in the plume. Analysis of the percent gasoline in the plume and accounting for weathering are steps to determining whether the lead content in an LNAPL plume is within the historical lead concentration ranges in gasolines. In addition to metals analyses, understanding of operational parameters such as the history of petroleum refining and handling operations, leaks, spills, and cleanup activities are needed for successful conclusion of the applicability of the petroleum exclusion.     

Polyaromatic hydrocarbon exposure: an ecological impact ambiguity

Polyaromatic hydrocarbons (PAHs) represent a fraction of petroleum hydrocarbons and are currently one of the foremost sources of generating energy in today’s contemporary society. However, evidence highlighted in this review show that PAH pollution, as a result of oil spills, hazardous PAH-contaminated working environments and technologies which do not efficiently utilise fuels, as well as natural sources of emissions (e.g. forest fires) may have significant health implications for all taxa. The extent of damage to organisms from PAH exposure is dependent on numerous factors including degree and type of PAH exposure, nature of the environment contaminated (i.e. terrestrial or aquatic), the ability of an organism to relocate to pristine environments, type and sensitivity of organism to specific hydrocarbon fractions and ability of the organism to metabolise different PAH fractions. The review highlights the fact that studies on the potential damage of PAHs should be carried out using mixtures of hydrocarbons as opposed to individual hydrocarbon fractions due to the scarcity of individual fractions being a sole contaminant. Furthermore, potential damage of PAH-contaminated sites should be assessed using an entire ecological impact outlook of the affected area.     

Photo-induced toxicity of PAHs to Hyalella azteca and Chironomus tentans: effects of mixtures and behavior

In the aquatic environment, polycyclic aromatic hydrocarbon (PAH) contamination can result from several anthropogenic sources such as petroleum runoff, industrial processes, and petroleum spills. When ultraviolet light (UV) is present at sufficient intensity, the acute toxicity of some PAHs to aquatic biota is greatly enhanced. This photo-induced toxicity of PAHs is directly influenced by the amount of PAH and by the level of UV intensity present in the aquatic environment. Thus, behavioral responses and habits that affect an aquatic organism's exposure to UV as well as exposure to PAHs can influence the extent to which damage due to photo-induced toxicity occurs. Experiments demonstrated the effects of photo-induced toxicity of anthracene and fluoranthene on the survival of two benthic macroinvertebrates, the midge Chironomus tentans and the freshwater amphipod Hyalella azteca. This study further investigated the survival and behavior of the test organisms in different substrates (no substrate, a sand monolayer, leaf discs, and sediment) with and without UV. The free-swimming, epibenthic H. azteca avoided the effects of photo-induced toxicity of PAHs to some extent by hiding in leaves when this substrate was available. Results emphasize the importance of organisms' behavior in affecting the photo-induced toxicity of PAHs in the aquatic environment.     

Treatment of Nonhazardous Petroleum-Contaminated Soils by Thermal Desorption Technologies

Spills, leaks, and accidental discharges of petroleum products have contaminated soil at thousands of sites in the United States. One remedial action technique for treating petroleum contaminated soil is the use of thermal desorption technologies.

This paper describes key elements of the U.S. Environmental Protection Agency report titled “Thermal Desorption Applications Manual for Treating Nonhazardous Petroleum Contaminated Soils.”¹ The applications manual describes the types, mechanical and operating characteristics of thermal desorption technologies that are commercially available to treat petroleum-contaminated soils. It also provides step-by-step procedures to rate the critical success factors influencing the general applicability of thermal desorption at a particular site. These factors include site, waste and soil characteristics, regulatory requirements, and process equipment design and operating characteristics. Procedures are provided to determine the types of thermal desorption systems that are most technically suitable for a given application and to determine whether on-site or off-site treatment is likely to be the most cost-effective alternative. Key factors that determine process economics are identified, and estimated cost ranges for treating petroleum-contaminated soils are presented. Spreadsheets are provided that can be used for performing cost analyses for specific applications.

The aforementioned report is applicable only to the treatment of petroleum-contaminated soils that are exempt from being classified as hazardous wastes under the Resource Conservation and Recovery Act (RCRA) or as toxic materials under the Toxic Substances Control Act (TSCA). Although much of the technical discussion in this paper is applicable to the treatment of both nonhazardous and hazardous ortoxic materials, permitting requirements and treatment costs are significantly different forthe individual categories of waste materials.     

Incineration of hazardous wastes from the petroleum industry in Nigeria

Persistent hazardous wastes are produced in the recovery, processing and upgrading of crude petroleum in Nigeria. However, recent developments in environmental pollution control are drawing increasing attention to the problems of hazardous wastes. The ever-increasing need to control these wastes from the petroleum industry often compels the chemical engineer to specify methods of treatment and disposal. Present methods for disposal are becoming increasingly undesirable for a number of reasons, and incineration is being considered as an alternative. This paper reviews the extent of hazardous waste generation from the Nigerian petroleum industry and its environmental implications. It also examines the current disposal methods and the incineration technology option. The major chemical engineering concepts of the incineration process and the principles guiding their operations are discussed. The potential for the use of incineration is examined, as well as information that would aid the choice of incineration system for new applications.     

Mercury burdens in Chinese mitten crabs (Eriocheir sinensis) in three tributaries of southern San Francisco Bay, California, USA

Chinese mitten crabs (Eriocheir sinensis), endemic to Asia, were first reported in the San Francisco Bay in 1992. They are now established in nearly all San Francisco Bay tributaries. These crabs accumulate more metals, such as mercury, than crustaceans living in the water column. Because their predators include fish, birds, mammals and humans, their mercury burdens have an exceptional potential to impact the ecosystem and public health. We sought to elucidate the potential threat of mitten crab mercury burdens in three adjacent streams in southern San Francisco Bay, one of which is known to be contaminated with mercury. Mitten crabs had hepatopancreas concentrations of total mercury and methylmercury that did not differ among streams. The maximum burden we measured was below the action level of 1 ppm recommended by the USEPA. Hepatopancreas concentrations of methylmercury declined with increasing crab size, suggesting a mechanism for mercury excretion and that predators might reduce mercury exposure if they select larger crabs. Because mercury may be heterogeneously distributed among tissues, estimation of the impacts of crab mercury burdens on the environment requires more data on the feeding preferences of predators.     

Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: concentrations, composition, and associated risks to protected sea otters

Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume ∼25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills.     

次级河流水污染事件应急处置程序及环境损害评估技术路线

近年来,随着我国经济的发展,次级河流突发性水污染事件频繁发生,对生态环境及居民生活造成了严重的影响。次级河流突发性水污染事件发生后,为减少污染造成的损失和影响,保证受损的环境资源得到恢复和补偿,不仅要立即采取行之有效的应急处置措施,而且应当积极开展环境损害鉴定评估工作,全面追究污染者的环境责任。根据次级河流本身的特点,结合各省市在环境应急处置过程中的具体做法,建立了一套应对突发性次级河流水污染事件的应急处置工作程序;阐述了环境损害鉴定评估的必要性、工作方法和技术路线,同时从受损环境资源的确认、污染源和污染物的识别以及暴露途径的建立3个方面构建了开展次级河流突发性水污染事件环境损害鉴定评估工作的因果关系链条,对实际开展相关工作具有重要意义。     

The Threats from Oil Spills: Now, Then, and in the Future

The ongoing oil spill from the blown-out well by the name of Macondo, drilled by the ill-fated rig Deepwater Horizon, has many features in common with another blowout in the Mexican Gulf that happened three decades ago. Then the oil gushed out from the Ixtoc I well drilled by the Sedco 135-F semi-submersible rig. In the years between these catastrophes, the source and nature of oil spills have undergone large changes. Huge spills from tankers that ran aground or collided used to be what caught the headlines and caused large ecological damage. The number and size of such accidental spills have decreased significantly. Instead, spills from ageing, ill-maintained or sabotaged pipelines have increased, and places like Arctic Russia, the Niger Delta, and the northwestern Amazon have become sites of reoccurring oil pollution. As for blowouts, there is no clear trend with regard to the number of incidences or amounts of spilled oil, but deepwater blowouts are much harder to cap and thus tend to go on longer and result in the release of larger quantities of oil. Also, oil exploration and extraction is moving into ever-deeper water and into stormier and icier seas, increasing potential risks. The risk for reoccurring spills like the two huge Mexican Gulf ones is eminent and must be reduced.     

Potential Air Emission Impacts of Cellulosic Ethanol Production at Seven Demonstration Refineries in the United States

Abstract

This paper reports on the estimated potential air emissions, as found in air permits and supporting documentation, for seven of the first group of precommercial or “demonstration” cellulosic ethanol refineries (7CEDF) currently operating or planning to operate in the United States in the near future. These seven refineries are designed to produce from 330,000 to 100 million gal of ethanol per year. The overall average estimated air emission rates for criteria, hazardous, and greenhouse gas pollutants at the 7CEDF are shown here in terms of tons per year and pounds per gallon of ethanol produced. Water use rates estimated for the cellulosic ethanol refineries are also noted. The air emissions are then compared with similar estimates from a U.S. cellulosic ethanol pilot plant, a commercial Canadian cellulosic ethanol refinery, four commercial U.S. corn ethanol refineries, and U.S. petroleum refineries producing gasoline. The U.S. Environmental Protection Agency (EPA) air pollution rules that may apply to cellulosic ethanol refineries are also discussed. Using the lowest estimated emission rates from these cellulosic ethanol demonstration facilities to project air emissions, EPA’s major source thresholds for criteria and hazardous air pollutants might not be exceeded by cellulosic ethanol refineries that produce as high as 25 million gal per year of ethanol (95 ML). Emissions are expected to decrease at cellulosic ethanol refineries as the process matures and becomes more commercially viable.     

Oil Contamination in Ogoniland, Niger Delta

The study shows extensive oil contamination of rivers, creeks, and ground waters in Ogoniland, Nigeria. The levels found in the more contaminated sites are high enough to cause severe impacts on the ecosystem and human health: extractable petroleum hydrocarbons (EPHs) (>10-C40) in surface waters up to 7420 μg L⁻¹, drinking water wells show up to 42 200 μg L⁻¹, and benzene up to 9000 μg L⁻¹, more than 900 times the WHO guidelines. EPH concentrations in sediments were up to 17 900 mg kg⁻¹. Polycyclic aromatic hydrocarbons concentrations reached 8.0 mg kg⁻¹, in the most contaminated sites. The contamination has killed large areas of mangroves. Although the natural conditions for degradation of petroleum hydrocarbons are favorable with high temperatures and relatively high rainfall, the recovery of contaminated areas is prevented due to the chronic character of the contamination. Oil spills of varying magnitude originates from facilities and pipelines; leaks from aging, dilapidated, and abandoned infrastructure; and from spills during transport and artisanal refining of stolen oil under very primitive conditions.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-013-0412-8) contains supplementary material, which is available to authorized users.     

Amazonian freshwater habitats experiencing environmental and socioeconomic threats affecting subsistence fisheries

Matching the trend seen among the major large rivers of the globe, the Amazon River and its tributaries are facing aquatic ecosystem disruption that is affecting freshwater habitats and their associated biodiversity, including trends for decline in fishery resources. The Amazon’s aquatic ecosystems, linked natural resources, and human communities that depend on them are increasingly at risk from a number of identified threats, including expansion of agriculture; cattle pastures; infrastructure such as hydroelectric dams, logging, mining; and overfishing. The forest, which regulates the hydrological pulse, guaranteeing the distribution of rainfall and stabilizing seasonal flooding, has been affected by deforestation. Flooding dynamics of the Amazon Rivers are a major factor in regulating the intensity and timing of aquatic organisms. This study’s objective was to identify threats to the integrity of freshwater ecosystems, and to seek instruments for conservation and sustainable use, taking principally fish diversity and fisheries as factors for analysis.     

Evaluation of surface water quality using an ecotoxicological approach: a case study of the Alqueva Reservoir (Portugal)

Background, aim, and scope  

Freshwater reservoirs can be impacted by several hazardous substances through inputs from agricultural activity, sewage discharges, and groundwater leaching and runoff. The water quality assessment is very important for implementation of the monitoring and remediation programs to minimize the risk promoted by hazardous substances in aquatic ecosystems. Evaluation of the degree of contamination of aquatic environments must not take in account only its chemical characterization but it must be complemented with biological assays, which determine potential toxic effects and allows an integrated evaluation of its effects in populations and aquatic ecosystem communities. The application of this type of strategy has clear advantages allowing a general evaluation of the effects from all the water components, including those due to unknown substances and synergic, antagonistic, or additive effects. There are only a few studies that reported ecotoxicological acute end points, for the assessment of surface water quality, and the relationship among toxicity results and the anthropogenic pollution sources and the seasonal period. The aim of this study was to assess the ecotoxicological characterization of the surface water from Alqueva reservoir (South of Portugal) and to evaluate the influence of anthropogenic sources of pollution and their seasonal variation in its toxicity. The construction of Alqueva reservoir was recently finished (2002) and, to our knowledge, an ecotoxicological assessment of its surface water has not been performed. Because of that, no information is available on the possible impact of pollutants on the biota. The surface water toxicity was assessed using acute and chronic bioassays. The results are to be used for developing a monitoring program, including biological methods.     

Distribution,sources, and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in surface water in industrial affected areas of the Three Gorges Reservoir,China

Water samples were collected from wastewater treatment plant (WWTP), drain water (DW), major tributaries (MT), and main course of the Yangtze River (MY) in areas of three industrial parks (IPs) in Chongqing city in the Three Gorges Reservoir (TGR). Sixteen EPA priority polycyclic aromatic hydrocarbon (PAH) pollutants were quantified to identify the effects of industrial activities on water quality of the TGR. The results showed that 11 individual PAHs were quantified and 5 PAHs (naphthalene (Nap), acenaphthylene (Acy), benzo[k]fluoranthene (BkF), indeno[1,2,3-cd]pyrene (InP), and benzo[g,h,i]perylene (BgP)) were under detection limits in all of the water samples. Three-ring and four-ring PAHs were the most detected PAHs. Concentrations of individual PAHs were in the range of not detected (nd) to 24.3 ng/L. Total PAH concentrations for each site ranged from nd to 42.9 ng/L and were lower compared to those in other studies. The mean PAH concentrations for sites WWTP, DW, MT, and MY showed as follows: DW (25.9 ng/L) > MY (15.5 ng/L) > MT (14.0 ng/L) > WWTP (9.3 ng/L), and DW contains the highest PAH concentrations. Source identification ratios showed that petroleum and combustion of biomass coal and petroleum were the main sources of PAHs. The results of potential ecosystem risk assessment indicated that, although PAH concentrations in MT and MY are likely harmless to ecosystem, contaminations of PAHs in DW were listed as middle levels and some management strategies and remediation actions, like strengthen clean production processes and banning illegal sewage discharging activities, etc., should be taken to lighten the ecosystem risk caused by PAHs especially risks caused by water discharging drains.     

Design a flower-like magnetic graphite carbon microsphere for enhanced adsorption of 2,4-dichlorophenol

Environmental Science and Pollution Research - 2,4-Dichlorophenol (2,4-DCP) is a hazardous chlorinated organic chemical, so its removal is an important task to protect the whole ecosystem and human...     

Release of vanadium from oxidized sediments: insights from different extraction and leaching procedures

Although the attention for vanadium (V) as a potentially harmful element is growing and some countries adopted threshold values for V in soils, sediments, groundwater, or surface water, V is generally of little importance in environmental legislation and the knowledge about the behavior of V in the environment is still limited. In the present study, the release of V from oxidized sediments, sediment-derived soils, and certified reference materials was investigated by means of several types of leaching tests and extractions that are frequently used for soil and sediment characterization. The pH_stat leaching tests and single and sequential extractions applied in this study show that V generally displays a very limited actual and potential mobility in sediment. “Mobile” V concentrations, as estimated by the amount of V released by a single extraction with CaCl₂ 0.01 mol L^?1, were low, even in the most contaminated sediment samples. Only under strongly acidifying conditions (pH 2), such as in the case of ingestion of soil or sediment or in accidental spills, a substantial release of V can be expected.