Sodium Naphthenate Research Articles

Structural analysis of petroleum acids in highly acidic crude oil and deacidification using organic amines

Naphthenic acids, polar compounds with carboxylic group, are commonly found in crude oils as product of biodegradation. The presence of NAs in oil can cause corrosion of processing equipment and pipelines and can lead to degradation of crude oil quality. Qilu high acid crude oil was designated for research, from which the acidic fraction was separated by caustic extraction. Elemental analysis, Fourier transform infrared spectroscopy, nuclear magnetic resonance and high-resolution Orbitrap mass spectrometry were used for characterization. The structure of the acidic fraction was verified to be naphthenic acids primarily, and the average molecular formula was obtained. Based on the derivation of the modified B-L method, the average molecular structure was monocycloalkyl benzoic acid with single carboxyl substitution The effects of various depickling solvents and process conditions on deacidification results as well as product were investigated and illustrated with potentiometric titration, UV spectroscopy, zeta potential test and Karl Fischer method. Among the three groups of deacidifiers, inorganic bases represented by sodium hydroxide have the best deacidification efficiency, reaching 83.5 %. But the emulsification caused by sodium naphthenate is severe and the emulsion is stable, making it difficult to achieve oil–water separation. Polyethylene polyamines cause the least emulsification. Moreover, as the number of amino groups in the monomer rises, the number of sites that can be neutralized with petroleum acids increases, and the deacidification rate rises. As result, the most suitable deacidifier for processing is ethanolamine, which can reduce the total acid number of crude oil to 0.47 after three stages of deacidification at 70 °C and a concentration of 10 %.

Removal of Excess Alkali from Sodium Naphthenate Solution by Electrodialysis Using Bilayer Membranes for Subsequent Conversion to Naphthenic Acids.

The processing of solutions containing sodium salts of naphthenic acids (sodium naphthenate) is in high demand due to the high value of the latter. Such solutions usually include an excessive amount of alkali and a pH of around 13. Bipolar electrodialysis can convert sodium naphthenates into naphthenic acids; however, until pH 6.5, the naphthenic acids are not released from the solution. The primary process leading to a decrease in pH is the removal of excess alkali that implies that some part of electricity is wasted. In this work, we propose a technique for the surface modification of anion-exchange membranes with sulfonated polyetheretherketone, with the formation of bilayer membranes that are resistant to poisoning by the naphthenate anions. We investigated the electrochemical properties of the obtained membranes and their efficiency in a laboratory electrodialyzer. Modified membranes have better electrical conductivity, a high current efficiency for hydroxyl ions, and a low tendency to poisoning than the commercial membrane MA-41. We propose that the primary current carrier is the hydroxyl ion in both electromembrane systems with the MA-41 and MA-41M membranes. At the same time, for the modified MA-41M membrane, the concentration of hydroxyl ions in the anion-exchanger phase is higher than in the MA-41 membrane, which leads to almost five-fold higher values of the specific permeability coefficient. The MA-41M membranes are resistant to poisoning by naphthenic acids anions during at least six cycles of processing of the sodium naphthenate solution.

Metabolomic Analysis of Hexagenid Mayflies Exposed to Sublethal Concentrations of Naphthenic Acid.

The oil sands region in northeastern Alberta, Canada contain approximately 165 billion barrels of oil making it the third largest oil reserves in the world. However, processing of extracted bitumen generates vast amounts of toxic byproduct known as oil sands process waters. Naphthenic acids and associated sodium naphthenate salts are considered the primary toxic component of oil sands process waters. Although a significant body of work has been conducted on naphthenic acid toxicity at levels comparable to what is observed in current oil sands process waters, it is also important to understand any impacts of exposure to sublethal concentrations. We conducted a microcosm study using the mayfly Hexagenia spp. to identify sublethal impacts of naphthenic acid exposure on the survival, growth, and metabolome across a concentration gradient (0–100 μg L−1) of sodium naphthenate. Nuclear magnetic resonance-based metabolomic analyses were completed on both the polar and lipophilic extracted fractions of whole organism tissue. We observed a positive relationship between sodium naphthenate concentration and mean principal component score of the first axis of the polar metabolome indicating a shift in the metabolome with increasing naphthenic acid exposure. Eleven metabolites correlated with increased naphthenic acid concentration and included those involved in energy metabolism and apoptosis regulation. Survival and growth were both high and did not differ among concentrations, with the exception of a slight increase in mortality observed at the highest concentration. Although lethal concentrations of naphthenic acids in other studies are higher (150–56,200 μg L−1), our findings suggest that physiological changes in aquatic invertebrates may begin at substantially lower concentrations. These results have important implications for the release of naphthenic acids into surface waters in the Alberta oil sands region as an addition of even small volumes of oil sands process waters could initiate chronic effects in aquatic organisms. Results of this research will assist in the determination of appropriate discharge thresholds should oil sands process waters be considered for environmental release.

Drainage via stratification and nanoscopic thickness transitions of aqueous sodium naphthenate foam films.

Sodium naphthenates (NaNs), found in crude oils and oil sands process-affected water (OSPW), can act as surfactants and stabilize undesirable foams and emulsions. Despite the critical impact of soap-like NaNs on the formation, properties, and stability of petroleum and OSPW foams, there is a significant lack of studies that characterize foam film drainage, motivating this study. Here, we contrast the drainage of aqueous foam films formulated with NaN with foams containing sodium dodecyl sulfate (SDS), a well-studied surfactant system, in the relatively low concentration regime (c/CMC < 12.5). The foam films exhibit drainage via stratification, displaying step-wise thinning and coexisting thick-thin regions manifested as distinct shades of gray in reflected light microscopy due to thickness-dependent interference intensity. Using IDIOM (interferometry digital imaging optical microscopy) protocols that we developed, we analyze pixel-wise intensity to obtain thickness maps with high spatiotemporal resolution (thickness <1 nm, lateral ∼500 nm, time ∼10 ms). The analysis of interference intensity variations over time reveals that the aqueous foam films of both SDS and NaN possess an evolving, dynamic, and rich nanoscopic topography. The nanoscopic thickness transitions for stratifying SDS foam films are attributed to the role played by damped supramolecular oscillatory structural disjoining pressure contributed by the confinement-induced layering of spherical micelles. In comparison with SDS, we find smaller concentration-dependent step size and terminal film thickness values for NaN, implying weaker intermicellar interactions and oscillatory structural disjoining pressure with shorter decay length and periodicity.

Risks of Mixtures of Oil Sands Contaminants to a Sensitive Mayfly Sentinel, Hexagenia

Tailings ponds in northeastern Alberta, Canada contain massive amounts of oil sands process water (OSPW) that cannot currently be released due to the toxicity of some components. Limited space and the need for reclamation of oil sands operation sites will necessitate the release of OSPW in the near future. Knowledge of the composition and toxicity of OSPW is lacking yet is crucial for both risk assessment and management planning. This study examines chronic toxicity of a mixture of OSPW components sodium naphthenate and naphthenic acid (NA) to nymphs of the mayfly Hexagenia spp. in control and polycyclic aromatic hydrocarbons (PAH)-spiked sediment treatments. The objective of this study was to determine whether the addition of the PAH-spiked sediment significantly contributed to or masked responses of these sensitive mayflies to mixtures of NA. Mean survival in nymphs exposed to NA and PAH-spiked sediment treatments was reduced by 48% compared to those exposed to the NA mixture alone. Lethal responses were observed in all of the PAH-spiked sediment treatments. However, within PAH-spiked and control sediment treatments, there was no significant difference in nymph survival due to NA concentration, indicating that changes in survivorship were predominantly a reflection of increased mortality associated with sediment PAHs and not to the NA mixture treatment. Sublethal effects on body segment ratios suggest that mayflies exposed to NA and PAH-spiked sediment, as well as those exposed to the highest NA concentration tested (1 mg/L) and control sediment, made developmental trade-offs in order to emerge faster and escape a stressful environment. These results reveal that the release of OSPW to the surrounding environment could cause a reduction in mayfly populations. Mayflies provide ecosystem services and are an important food source for higher trophic levels in both the aquatic and terrestrial communities.

RHEOLOGICAL PROPERTIES OF CERAMIC MASSES: IMPROVEMENT BY COMPLEX MATERIAL ACTIVATION

Introduction. The objective of the research is to study the effect of the complex activation of the alumina raw material on the rheological properties of the ceramic mass. In addition, the authors investigate solutions for the application of optimal coagulation structures based on loams and ash together with plastic certificates.Materials and methods. The authors used the local forest like reserves of clay loams at the BashKarasu, ash fields of the Bishkek Central Heating Centre (BTEC) and plasticizer (sodium naphthenate obtained from alkaline chemical production wastes) as fibrous materials. Moreover, the authors defined technological properties of raw materials within standard laboratory methodology in accordance with current GOSTs.Results. The researchers tested plastic durability on variously prepared masses for the choice of optimal structures. The paper demonstrated the plastic durability of complexly activated compounds comparing with non-activated and mechanically activated compounds. The sensitivity coefficient increased the amount of clay loams by mechanically and complexly activated, which predetermined the possibility of intensifying the process of drying samples based on complexly activated masses.Discussion and conclusions. However, mechanical activation of clay material reduces the period of relaxation and increases the elasticity coefficient of ceramic masses by 1.8–3.4 times, meanwhile decreases elasticity, viscosity and the conventional power during molding, which generally worsens the molding properties of the masses. Сomplex activation of ash-clay material decreases the period of relaxation and provides an increase in elasticity, plasticity of ceramic masses by 46–47%, reduction in viscosity by 1.5–2 times, conventional power on molding by 37–122% in comparison with MA clay loams. Ceramic masses based on spacecraft alumina raw materials belong to the SMT with improved rheological properties; products based on them pass through the mouthpiece for 5–7 seconds.

Effects of oil sands process water mixtures on the mayfly Hexagenia and field-collected aquatic macroinvertebrate communities.

Extraction of Canada's oil sands has created 1 billion m3 of tailings, which are stored in on-site tailings ponds. Due to limited storage capacity, the planned release of tailings into the surrounding environment may be required. This represents an environmental management challenge, as the tailings contain contaminants that are known toxins to aquatic communities. Of particular concern are naphthenic acids and their metallic counterparts, as they are the principal toxic components of tailings, are relatively soluble, and are persistent in aquatic environments. This study examines the acute toxicity of environmentally relevant 10:1 mixtures of two process water components: naphthenic acid and sodium naphthenate. We assess the effects of these simplified oil sands process water (OSPW) mixtures under planned and unplanned tailings release scenarios, using traditional and cutting-edge bioindicators for aquatic invertebrate taxa. We found that safe concentrations for mayflies and other aquatic macroinvertebrates were less than 1 mg/l, as no mayfly taxa survived repeated exposure to this dose in either the 48-h or 72-h acute toxicity test. In the 72-h test, no mayflies survived treatment levels greater than 0.5 mg sodium naphthenate/l. In the mesocosm study, even a 90% dilution of the OSPW mixture was not sufficient to protect sensitive macroinvertebrate communities. The results of this study highlight the potential environmental damage that will occur if OSPW is not carefully managed. This information will aid with the development of a management plan for oil sands tailings ponds, which will provide insight into the potential for process water release into the surrounding environment while conserving unique ecosystems downstream of development in the oil sands region.

Exchange Sorption and Electrical Conductivity of Heterogeneous Anion-Exchange Membranes in Mixed Sodium Hydroxide/Sodium Naphthenate and Sodium Sulfate/Sodium Nitrate Electrolyte Solutions

The physicochemical properties of MA-40 and MA-41 ion-exchange membranes have been studied in two systems with different electrolyte compositions. The following test systems have been chosen for the study: anion-exchange membrane/mixed solution of sodium hydroxide and sodium naphthenate and anion-exchange membrane/mixed solution of sodium sulfate and sodium nitrate. Ion-exchange sorption and electrical conductivity have been studied in these systems. It has been found that both of the membranes are more selective for hydroxide ions than for naphthenic acid anions in the system with sodium naphthenate. A conductor–insulator percolation transition has been observed in the МА-40 and MA-41 membranes saturated with organic counterions. The mobilities and diffusion coefficients of hydroxide, nitrate, and sulfate ions in the test membranes haves been calculated.

The Increased Content of Micronutrients in Celery, Carrot, Parsnip and Parsley Plants after Treatment with Sodium Naphthenate

Summary Young plants of celery, parsley, parsnip and carrot, grown in nutrient solution, were treated with sodium naphthenate (10−7 mol dm−3), applying foliar and root treatments. Both treatments affected the root content of all investigated elements present in the nutrient solution, but in a different way, depending on the plant species. An average change (increase/decrease) in the contents of investigated essential elements was about 35%. Our experiments with naphthenate showed that this treatment may enhance the efficiency of essential elements uptake and increase its content in plants without changing concentration of these elements in the nutrient solution. Especially interesting results were obtained in the case of carrot, as increased contents were observed in the elements that are usually deficient in nutrition (Fe, Zn, Mn), whereas the other remained unchanged.

The influence of naphthenic acids and their fractions onto cell membrane permeability

The influence of naphthenic acids (NAs) mixture and their narrow fractions (called NA pH 4, pH 8 and pH 10) onto permeability of beetroot cell membrane is examined. The results showed that the effect depends on treatment duration, concentration and NAs structure. Longer treatment of plant cell membranes with sodium naphthenate (Na-naph) resulted in the increase of membrane permeability (e.g. 4-hour treatment with Na-naph (C=100 ?mol L-1) increased membrane permeability about 3 times, while prolongation of treatment to 24 hour resulted in the 18 times increasing of the effect). NAs in the concentration range from 0.1 to 10 ?mol L-1 does not change membrane permeability, while membrane permeability is increasing linearly with concentration increasing from 10-100 ?mol L-1. The strongest effect expressed fraction pH 8, where bi- and tricyclic carboxylic acids are the most abundant. These structures are predominant in the total NAs mixture as well. Thereby could be explained their closest, but a little bit weaker effect, comparing to NAs present in fraction pH 8. The effect of NAs onto beetroot cell membrane is between the effects of anionic (SDS and LS) and non-ionic surfactants (Triton X-100).

Comparison of sodium naphthenate and air-ionization corona discharge as surface treatments for the ethylene-tetrafluoroethylene polymer (ETFE) to improve adhesion between ETFE and acrylonitrile-butadiene-styrene polymer (ABS) in the presence of a cyanoacrylate adhesive (CAA)

This study compares two ethylene-tetrafluoroethylene (ETFE) surface activation treatments, namely chemical attack with a solution of sodium naphthenate and plasma erosion via air-ionization corona discharge in order to improve the adhesive properties of the ETFE. An experimental design was prepared for both treatments in order to assess the effect of the treatment characteristics on the tensile load needed to break the bond between the ETFE and the acrylonitrile-butadiene-styrene polymer (ABS) formed with a cyanoacrylate adhesive (CAA) applied between them. The reason for the selection of this problem is that both polymers are frequently used in the biomedical industry for their properties, and they need to be joined firmly in biomedical devices, and the cyanoacrylate adhesive is the adhesive traditionally used for fluoropolymers, in this case the ETFE, and the same CAA has also shown good adhesion with ABS. However, the strength of the bond for the triplet ETFE-CAA-ABS has not been reported and the improvement of the strength of the bond with surface treatments is not found in scholarly journals for modern medical devices such as stents and snares. Both treatments were compared based on the aforementioned design of experiments. The case where ETFE receives no surface treatment serves as the reference. The results indicated that the three factors evaluated (initial drying of the material, temperature of the chemical bath, and immersion time), and their interactions have no significant effect over the tensile load at failure (tensile strength) of the adhesive bond being evaluated. For the air-ionization corona discharge treatment, two factors were evaluated: discharge exposition time and air pressure. The results obtained from this experimental design indicate that there is no significant difference between the levels of the factors evaluated. These results were unexpected as the ranges used were representative of the maximum ranges permissible in manufacturing operations. As for the comparison of the treatments, it was determined that the treatments have statistically significant differences. It was also determined that there is a significant statistical difference between the processes where a surface treatment is performed and the process where no surface treatment is applied to the ETFE. The chemical treatment results in a higher tensile load at failure (tensile strength) of 276.6 N on average, the air ionization treatment has an average of 248.4 N, and the process with no treatment has the lower ultimate tensile strength average of 53 N. This comparison has demonstrated that the best treatment is the chemical treatment with sodium naphthenate under the conditions tested.

Effects of Non-Ionic Surfactant on the Deep Temperature Flotation Agents of Hematite

This investigation involves the effects of non-ionic surfactant materials on the industrial sodium oleate, sodium naphthenate and their mixtures at different temperatures by the surface tension methods. The effects on the critical micelle concentration (CMC) of sodium oleate were assessed by the Toween 80(T-80) presence, polyethylene glycol, polyether and other non-ionic surfactant. T-80 was proved more effective than other non-surfactant in increasing the sodium oleate CMC at same concentration. Using the optimal composition of sodium fatty acid and the surfactant can reduce the temperature of separation hematite from 43°C to 23°C, achieve the purpose of low carbon and energy saving.

Interactions of divalent cations with tetrameric acid aggregates in aqueous solutions

Interactions in aqueous solutions between a tetrameric naphthenic acid in sodium salt (BP10Na4) and divalent Mg2+ and Ca2+ cations were investigated by isothermal titration calorimetry (ITC) and dynamic light scattering (DLS). Colloidal aggregation of the tetrameric sodium naphthenates to vesicles and micelles enhances its binding with divalent cations. In vesicle systems, Ca2+ was found to bind first with carboxylate groups located at the external water/lipid interface of vesicles. The cations then diffuse through the membrane to interact with the inner carboxylate groups. Higher Ca2+ concentration and higher salinity gradients enhance cation diffusion. Under solution chemistry conditions where micelle dominates, Ca2+ reacts only with outer carboxylate groups of BP10Na4 without any significant cation diffusion through the aggregates. The binding of calcium with sodium naphthenate is an entropy-driven process where entropy gain comes from the dehydration of both cations and carboxylate groups of BP10Na4. The affinity of Mg2+ to BP10Na4 is much weaker than Ca2+ due to its stronger hydration and hence larger size of hydrated magnesium ions than hydrated calcium ions.

Wettability Alteration of Clay in Solid-Stabilized Emulsions

Processing of bitumen froth obtained from surface mining process of Athabasca oil sands yields stable water-in-diluted bitumen emulsions. Even with a demulsifier, a “rag layer” forms between the oil and free water layers when clay solids are present. Experiments reveal that wettability of clay solids has a significant effect on emulsion stability. Kaolinite in toluene–brine mixture was chosen as model system to study clay wettability alteration related to emulsion separation in bitumen froth treatment. Sodium naphthenate was added to simulate the presence of naphthenic acid in diluted bitumen. The fraction of the kaolinite that settled to the bottom of the aqueous phase was measured, and was referred to as “water-wet fraction”, to characterize the wettability of kaolinite. Without any additives, 96% of the kaolinite was water-wet. Addition of only 100 ppm sodium naphthenate reduced the water-wet fraction to only 18%. Wettability of kaolinite was altered by pH control, silicate, and surfactant under different mechanisms. Addition of 366 ppm silicate at pH 10 resulted in 80% of kaolinite being water-wet. To prevent emulsion formation at high pH, cationic and amphoteric surfactants were evaluated as an alternative to alkali. Over 90% of kaolinite became water-wet when adding alkyl quaternary ammonium bromide, betaine, or amine oxide with optimal dosages.

Effect of surfactants on interfacial films and stability of water-in-oil emulsions stabilized by asphaltenes

The effect of additives on asphaltene interfacial films and emulsion stability was analyzed through the change in film properties. Surface pressure isotherms were measured at 23°C for model interfaces between aqueous surfactant solutions and asphaltenes dissolved in toluene and heptane-toluene mixtures. Compressibility, crumpling film ratio and surface pressure were determined from the surface pressure isotherms. The stability of water-in-oil emulsions was determined for the same systems based on the proportion of unresolved emulsified water after repeated treatment involving heating at 60°C and centrifugation. Experimental variables included concentration of asphaltenes (5 and 10 kg/m(3)), concentration and type of surfactant (Aerosol OT, nonylphenol ethoxylates, polypropylene oxide block-copolymer, dodecylbenzene sulfonic acids, dodecylbenzene sulfonic acid-polymer blend, diisopropyl naphthalene sulfonic acid, and sodium naphthenate) and aging time (from 10 min to 4 h). Additives were found to have two opposing effects on film properties and emulsion stability: (1) decreasing or eliminating the crumpling ratio which destabilized emulsions and (2) decreasing interfacial tension which enhanced emulsion stability. A stability parameter was defined to include both the crumpling ratio and interfacial tension and provided a consistent correlation for the percent residual emulsified water.

Characterization of naphthenic acids in crude oils and naphthenates by electrospray ionization FT-ICR mass spectrometry

We present the selective ionization of acidic components of crude oils and naphthenates by negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We further characterize isolated naphthenic acids from a calcium napthenate deposit by negative-ion ESI tandem mass spectrometry (MS n): collision-induced dissociation (CID) and infrared multiphoton dissociation (IRMPD). Selective ionization by electrospray affords direct characterization of neutral nitrogen species and naphthenic acids in petroleum without derivatization or preconcentration of the sample, and with minimal sample consumption. Acids isolated from a calcium naphthenate deposit are tetraprotic with a C 80 hydrocarbon skeleton; commonly known as “ARN” acids, whereas sodium naphthenate consists of low molecular weight (C 15 to C 35) linear saturated monoprotic carboxylic acids. IRMPD and CID fragmentation of ARN acids result in both dehydration and decarboxylation of the carboxylic acid groups without dealkylation. However, CID produced more extensive fragmentation leading to dealkylation of the hydrocarbon skeleton. The ultrahigh resolution and mass accuracy of FT-ICR MS and MS/MS provide for detailed identification and compositional differences of acidic species in crude oils and naphthenates, and also afford structural characterization of acids isolated from naphthenate deposits.

Chemical Speciation of Calcium and Sodium Naphthenate Deposits by Electrospray Ionization FT-ICR Mass Spectrometry

Calcium and sodium naphthenates are solid deposits and emulsions formed by the interaction of naphthenic acids with divalent (Ca2+, Mg2+) or monovalent (Na+, K+) ions in produced waters. Calcium naphthenate formation, an interfacial phenomenon, is thought to depend largely on tetraprotic naphthenic acids known as “ARN” acids (∼C80) in the crude oil, whereas sodium naphthenates originate from lower molecular weight (C15 to C35) monoprotic naphthenic acids. Here we present detailed chemical heteroatom class composition analyses of calcium and sodium naphthenates from the field based on high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). In all cases, calcium naphthenate deposits consist predominately of tetraprotic acids with a C80 hydrocarbon skeleton whereas sodium naphthenate emulsions consist mainly of specific monoprotic saturated carboxylic acids. Furthermore, low molecular weight tetraprotic (ARN) acids with C60−77 hydrocarbon skeletons were identified in the calc...

The Characteristic Curvature of Ionic Surfactants

AbstractCharacterizing the hydrophilic‐lipophilic nature of a surfactant molecule has been a challenge for colloid scientists and technologists. The hydrophilic‐lipophilic balance (HLB), the packing factor, the phase inversion temperature (PIT) and the natural curvature of the surfactant are all terms that seek to address this issue. In this article we build on the hydrophilic–lipophilic difference concept (HLD) (Salager et al. Langmuir, 16, 5534–5539, 2000) to develop a methodology to determine a characteristic curvature (Cc) for ionic surfactants based on the phase behavior of mixed ionic surfactant microemulsions. In essence, the method consists of evaluating the shift in optimal electrolyte concentration as a function of the mole fraction of the test surfactant in a mixture with a reference surfactant, sodium dihexyl sulfosuccinate (SDHS) and applying the appropriate HLD equation for ionic surfactant mixtures to determine Cc. The values of Cc were determined for a range of surfactants, including sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), sodium naphthenate, and others. The method was also extrapolated to nonionic additives and hydrophilic linkers. It was observed that the calculated values of Cc were similar to those predicted by group contribution models, however the proposed method can be used even for complex surfactant mixtures. Finally, when Cc values were compared to apparent packing factor and HLB values, it was found that Cc is correlated with the apparent packing factor of ionic surfactants, and that Cc correlates with the HLB value for nonionic amphiphiles. The physical interpretation of Cc, and its potential application in the Net‐Average Curvature equation of state for oil‐surfactant‐water systems is discussed.

Effects of oil sands process-affected waters and naphthenic acids on yellow perch (Perca flavescens) and Japanese medaka (Orizias latipes) embryonic development

Syncrude Canada Ltd. is currently developing environmentally acceptable oil sands process-affected water management methods as part of their land reclamation strategy. Surface waters of the "wet landscape" reclamation option characteristically have elevated concentrations of sodium sulphate and naphthenic acids (NAs), with low levels of PAHs. The following experiment compared early-life stage responses of yellow perch (Perca flavescens) to those of Japanese medaka (Oryzias latipes) when exposed to Mildred Lake settling basin (MLSB) surface water and a commercial sodium naphthenate (Na-NA) standard. Perch eggs were fertilized and incubated in: 100%, 50%, 20%, 4%, 0.8%, and 0.16% dilutions of MLSB water, as well as 20, 10, 5, 2.5, and 1.25 mg/l solutions of the commercial standard. Medaka embryos were exposed to the same treatments, post-fertilization. Both species demonstrated an increase in the incidence of deformity, and a decrease in length at hatch as NA concentrations increased. MLSB surface water contained higher levels of NAs than the commercial standard, however, showed consistently higher NA threshold effect concentrations for both species. Significant differences between the MLSB water and the Na-NA standard suggest that they contain NA congeners with different toxicity, or other compounds such as PAHs. Species differences in thresholds could be explained by the difference in developmental stage in which the exposures were initiated.

Biochemical changes in cuttings of Robinia pseudoacacia after treatment with naphthenate

Naphthenic acids were isolated from gas oil fractions (distillation interval 168-290?C) of Vojvodina crude oil "Velebit", characterized and their biological activity evaluated by the biochemical changes in cuttings of Robinia pseudoacacia after treatment with naphthenate. The activities of IAA peroxidase, total peroxidases and amylase, as well as the contents of reducing sugars and total proteins, were determined in the basal parts of soft wood cuttings of black locust after treatment with sodium naphthenate or the sodium salt of 1-naphthaleneacetic acid (NAA), concentration 10-7 mol dm-3 for 3 or 6 h. High activities of IAA oxidase and amylase, together with a low activity of peroxidase (which is known as being stimulatory for the initiation and activation of primordia) were obtained after the three-hour treatment with sodium naphthenate. Six-hour treatment had an inhibitory effect on the examined biochemical markers. The effects of three- and six-hour treatments with NAA were between those of the corresponding treatment with naphthenic acids. .