Application of ultrasonic assisted extraction of chemically diverse organic compounds from soils and sediments

The objective of this research was the development, optimization, and demonstration of an ultrasonic assisted extraction (UAE) based method for organic anthropogenic waste indicators (AWIs) with a range of physicochemical properties from soil and sediment samples. The optimized method was designed to be cost effective compared to existing extraction methods, which may require large quantities of consumables, produce substantial volumes of organic waste, or require costly instrumentation or equipment. Reagent grade sand, soil collected from the native grassland in proximity to Eastern Washington University (EWU), and sediment samples collected from the Spokane river were used as sample matrices during method development. These matrices were fortified with eight AWIs of varying chemical properties that are representative of a variety of household, industrial, and agricultural sources. The recoveries of the AWIs spiked onto these matrices were determined in the extracts using gas chromatography/mass spectrometry (GC/MS). These values reflect the efficiency of the method for extraction of these analytes from representative environmental matrices. Recoveries ranged from 46.1% to 110% in the fortified soil and from 49.2% to 118.6% in the fortified sediment samples, which is comparable with existing methods for the study analytes. The optimized method was then used to quantify AWIs in a biosolid-amended soil. Indole and p-cresol were detected in the biosolid-amended soil.     

Metal bioavailability and toxicity through a sediment core.

Sediment cores from Richard Lake near Sudbury, Ontario, were sectioned and analyzed for total metal content, plus metal bioavailability and toxicity to Hyalella azteca (after equilibration with oxygenated overlying water). Strong and similar sediment profiles were observed for Cd, Co, Cu and Ni in the sediment. However, these differed from metal bioavailability profiles (bioaccumulation by Hyalella and metals in overlying water). Bioavailability profiles for Cu also differed from those for Cd, Co or Ni. The deepest sediment layers, deposited prior to industrial development, were non-toxic. Sediment toxicity was attributed to Ni dissolution into overlying water. Moreover, differential bioavailability of Ni in surface and deeper sediment layers was observed. This can affect the interpretation of toxicity data for sediments collected by different methods (e.g. core vs. grab samples). Based on Pb-210 dating and trends in Ni in the core, chronic toxicity of surface sediments from Richard Lake might approach non-toxic levels in about 15 years.     

Isolation and characterization of naphthenic acids from Athabasca oil sands tailings pond water

A laboratory bench procedure was developed to efficiently extract naphthenic acids from bulk volumes of Athabasca oil sands tailings pond water (TPW) for use in mammalian oral toxicity testing. This solvent-based procedure involved low solvent losses and a good extraction yield with low levels of impurities. Importantly, labour-intensive centrifugation of source water to remove solids was avoided, allowing processing of much larger volumes of water compared with previous protocols. Naphthenic acids, present at an estimated concentration of 81 mg/l, were procured from 515.5 l of TPW at an overall extraction efficiency of approximately 85%. By using distillation to recover and recycle solvent, a high solvent:water ratio was maintained while actual solvent consumption was limited to 70 ml per liter of water processed. Electrospray ionization mass spectrometry suggested a highly heterogeneous naphthenic acid mixture that exhibited nearly identical proportions of monocyclic, polycyclic, and acyclic acids with molecular weights primarily between 220 and 360. Biphenyls, naphthalenes, and phenanthrene/anthracene were the most prominent impurities detected, but their levels were low (< or = 13 microg/l) even in a concentrated solution of the naphthenic acids (8549 mg/l). Naphthenic acids stored at 4 degrees C at this concentration were stable, exhibiting no significant change in concentration over a 10-month period. This bulk isolation procedure should be useful to others needing to process large volumes of tailings or other source water for the purpose of procuring moderate amounts of naphthenic acids.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Sediment quality in littoral regions of the Gulf of Cádiz: a triad approach to address the influence of mining activities

To evaluate sediment quality in different areas in the Gulf of Cádiz affected by mining activities, an integrative approach to assessment was used: the Sediment Quality Triad (SQT). Sediment samples were collected at six stations and subjected to replicated sediment acute and chronic toxicity tests, and comprehensive sediment chemistry analyses. Organisms collected synoptically at the same stations were analyzed for histopathological lesions and chemical concentrations in their tissues to determine 'in situ' alteration and bioavailability, in place of benthic community structure. The results obtained for each component were linked to the SQT using different methodologies of interpretation and expression of the integrated approach: (a) multivariate analysis, (b) significant statistical differences compared to the reference stations, (c) ANOVA-based pie charts, and (d) classical methods using triangles and the SQT index of pollution. SQT results indicated that the highest pollution was mainly associated with metals from mining activities and polyaromatic hydrocarbons in the Ría of Huelva. The use of histopathological measures and bioaccumulation of metals, improved the characterization of 'gray areas' of pollution and in the determination of the bioavailability of metals.     

Analyzing sediment dissolved oxygen based on microprofile modeling

Sediment plays a key role in controlling the oxygen demand of aquatic systems. The reaction rate, penetration depth, and flux across the sediment–water interface (SWI) are important factors in sediment oxygen consumption. However, there were few methods to collect these data until recently. In this study, methods were developed to simulate the oxygen microprofile and calculate the sediment oxygen consumption rate, oxygen penetration depth, and oxygen flux across the SWI. We constructed a sediment oxygen measuring system using an oxygen microelectrode and a control device. The simulation equations were derived from both zero and first-order kinetic models, while the penetration depth and the oxygen flux were calculated from the simulation results. The method was tested on four prepared sediment samples. Decreases in dissolved oxygen in surface sediment were clearly detected by the microelectrode. The modeled data were a good fit for the observed data (R ²?>?0.95), and zero-order kinetics were more suitable than first-order kinetics. The values for penetration depth (1.3–3.9 mm) and oxygen fluxes (0.061–0.114 mg/cm²/day) calculated by our methods are comparable with those from other studies.     

Nickel partitioning in formulated and natural freshwater sediments

A natural, field-collected sediment high in organic carbon (OC) and low in acid-volatile sulfide (AVS) was used to evaluate nickel (Ni) complexation to organic matter (OM) over a range of pH under anoxic conditions. It was found that OM strongly influenced Ni partitioning and that Ni complexation to OM was significantly influenced by pH, with complexation increasing with increasing pH (from pH 6 to 8). Using an equilibrium partitioning approach incorporating both [SEM(Ni)]-[AVS] and OC content, lethal and non-lethal toxicity test endpoints were calculated (predicted) and compared to observed toxicity test results using the amphipod, Hyalella azteca, exposed to four Ni-spiked natural sediments varying in OC and AVS content. Generally, lethal and non-lethal toxicity test endpoints were reasonably predictable in low AVS sediments. Due to the apparent lack of equilibrium between dissolved pore-water Ni and the pure Ni sulfide (likely the result of additional dissolved metal binding ligands), and the possible competition of liberated Fe2+ with Ni2+ for binding sites on organic matter, toxicity predictions (based on sediment OC and AVS content) overestimated the combined protective effects of AVS and OC in the sediments containing mid to high (27.87-44.05 micromol/g d.w.) AVS concentrations. Overall, it was found that equilibrium partitioning-based sediment quality guidelines can be improved through the incorporation of nickel complexation to sedimentary OM (in addition to AVS), although further research is required to fully describe nickel-OM interaction.     

Passaic river sediment interstitial water phase I toxicity identification evaluation

A suite of tests was conducted to evaluate and identify the cause or causes of toxicity in Passaic River sediments. Sediment toxicity was measured with three types of bioassays: a whole sediment bioassay with the marine amphipod, Ampelisca abdita, and interstitial water bioassays with A. abdita and the bioluminescent bacterium Vibrio fisheri (Microtox((R))). In addition, a Phase I Toxicity Identification Evaluation (TIE) was conducted to elucidate the cause of observed toxicity. Analytical concentrations of selected residues in whole sediment and interstitial water from the five sampling stations were considered in conjunction with the conclusions drawn from the toxicity tests and Phase I TIE results. Finally, a toxic units approach was used to evaluate the predicted toxicity of measured interstitial water residue concentrations. There was a lack of toxic response in the short-term interstitial water bioassays, indicating that oxidants, soluble forms of metals, and dissolved phase neutral organics were not likely toxicants. However, there was significant toxicity indicated by the whole sediment A. abidita bioassays. After 10 days, there was complete or near complete mortality in amphipods exposed to all of the sediment samples tested. Removal of interstitial water toxicity by filtration was common to all four stations that exhibited measurable initial toxicity. The observed toxicity characteristics are consistent with particle associated neutral organics. This conclusion is supported by toxicity removal via filtration, lack of toxicity in the Microtox((R)) assays, and the fact that whole sediments were more toxic than was interstitial water.     

Integrative assessment of marine pollution in Galician estuaries using sediment chemistry,mussel bioaccumulation,and embryo-larval toxicity bioassays

An integrative assessment of environmental quality was carried out in selected sites along the Galician coast (NW Iberian Peninsula) combining analytical chemistry of seawater and sediments, bioaccumulation in the marine mussel, and embryo-larval sediment toxicity bioassays, in order to link biological and chemical criteria for the assessment of coastal pollution. Maximum values of Hg and Cu in seawater, sediment and mussels, were found in the inner part of Ria of Pontevedra, while maximum levels of organics (polychlorinated biphenyls, hexachlorobenzene and aldrin) were found in mussels from A Coru?a. Outstanding values of Cu, Pb and Zn have been found in seawater and sediment from a single site, P3, which also was the most toxic in the embryo-larval bioassays performed with four different phyla of marine organisms: mollusks, echinoderms, arthropods and chordates. Sediment quality effects range-median values provided a valuable reference to predict biological effects from sediment chemistry data, while effects range-low values were too conservative. Sediment toxicity could also be predicted by using a toxic-unit model based on published EC50 values for trace metals and mobilization factors independently obtained from measurements of metal contents in sediments and their elutriates. When chemical and toxicological data are independently used to arrange sampling sites by using non-metric multidimensional scaling, a remarkable degree of concordance between both types of configurations could be observed.     

Do differences between metal body residues reflect the differences between effects for Chironomus riparius exposed to different sediments?

Sediment characteristics are well known to interfere with toxicity, mainly through differences in terms of bioaccumulation. Here, with chironomids exposed to zinc in an artificial and a field sediment, we investigated the differences of zinc accumulation and of effects on the life cycle, at individual and population level. We used biology and energy-based modeling to analyze the data at all the levels of biological organization. This permits a reliable estimation of thresholds values for tissue residues. Differences in zinc tissue residues accounted for most of the differences between the results for both sediments (a factor of 11 for differences from 20 to 100 depending on the parameter which is considered). Taking into account accumulation and background variability, the differences relative to thresholds could be accounted for. However, it appeared that, once the threshold was passed, effects were much more pronounced for organisms exposed to artificial sediment compared to field sediment. We concluded that some sediment characteristics can enhance toxicity, in addition to their influence on the compound accumulation, even if the latter was the major source of differences in our study.     

Quantification of bioavailable nickel in sediments and toxic thresholds to Hyalella azteca

Bioaccumulation and chronic toxicity of nickel (Ni) to Hyalella azteca in Ni-spiked sediments was strongly affected by the source of sediment used. The total range in LC50s on a sediment concentration basis ranged over 20 fold. Differences in Ni toxicity generally matched differences in Ni bioaccumulation, and toxicity expressed on a body concentration basis varied less than three fold. Body concentrations, therefore, provide a much more reliable prediction of Ni toxicity in sediments than do concentrations in the sediment. Ni in overlying water was also a reliable predictor of Ni toxicity, but only in tests conducted in Imhoff settling cones with large (67:1) water to sediment ratios. Overlying water LC50s for tests in beakers varied 18 fold. Sediment and body concentrations of Ni tolerated by Hyalella were slightly higher in cones than in beakers. Reproduction was not affected significantly by Ni at concentrations below the LC50 and 10-week EC50s for survival and biomass production (including survival, growth and reproduction) were only marginally lower than 4-week EC50s (survival and growth only).     

Estrogenicity profile and estrogenic compounds determined in river sediments by chemical analysis, ELISA and yeast assays

An effects-directed strategy was applied to bed sediments of a polluted tributary in order to isolate and identify the major estrogenic chemicals it discharges into the River Po, the principal Italian watercourse. Sediment extract was concentrated by solid phase extraction and then fractioned into 10 fractions by reversed phase high performance liquid chromatography (RP-HPLC). Estrogenic activity of whole extract and fractions were determined using a recombinant yeast assay containing the human estrogen receptor (YES). The 10 fractions and whole extract were analysed for target compounds, e.g. estrone (E1), 17beta-estradiol (E2), estriol (E3), 4-nonylphenol (NP), 4-tert-octylphenol (t-OP), bisphenol A (BPA), using both liquid chromatography-tandem mass spectrometry (LC-MS/MS) and non-competitive enzyme-linked immunosorbent assays (ELISA). The YES assay determined high estrogenic activity in whole sediment (15.6 ng/g EE2 equivalents), and positive results for fractions nr 1, 2, 6, 7 and 8. E1, E3 and NP were the main estrogenic chemicals, however, other unidentified compounds contributed to sediment estrogenicity, particularly for polar fractions nr 1 and 2. A GC-MS screening performed in scan mode identified other potential contributors such as phthalates (DBP, BBP), and OP isomers. A next sampling campaign extended to other tributaries and receiving stretches of the River Po confirmed E1, E3 and NP as major estrogenic chemicals potentially threatening other sites of the main river. In general, target compound ELISAs have been shown to be suitable tools for a rapid screening of wide areas or large numbers of environmental samples for estrogenic risk. The potential for interferences suggests however to use cautiously the concentration values obtained from some of the immunoassays.     

Sampling method, storage and pretreatment of sediment affect AVS concentrations with consequences for bioassay responses

Sediment treatment and sediment storage may alter sediment toxicity, and consequently biotic response. Purpose of our study was to combine these three aspects (treatment-toxicity-biotic response) in one integrated approach. We used Acid Volatile Sulfide (AVS) concentrations as a proxy of the disturbance of the sediment. AVS and Simultaneously Extracted Metal (SEM) concentrations were compared to bioassay responses with the freshwater benthic macroinvertebrate Asellus aquaticus. Storage conditions and sediment treatment affected AVS but not SEM levels. AVS can be used as a proxy for sediment disturbance. The best way to pretreat the sediment for use in a bioassay in order to maintain initial AVS conditions was to sample the sediment with an Ekman grab, immediately store it in a jar without headspace, and freeze it as soon as possible. In a survey using seven different sediments, bioassay responses of A. aquaticus were correlated with SEM and AVS characteristics.     

Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.     

The SeKT joint research project: definition of reference conditions, control sediments and toxicity thresholds for limnic sediment contact tests

- In current biotest approaches, intact organisms or in vitro systems are exposed to sediments using different exposure scenarios. The most important issue in sediment toxicity testing protocols is the question which test phase (solid or liquid) should be used. Whole-sediment exposure protocols represent the most realistic scenario to simulate in situ exposure conditions in the laboratory. However, until now there is no agreement in how to acquire and to evaluate the data of the various available sediment contact assays. The SeKT joint research project was initiated with the aim to compare recently developed sediment contact assays by addressing reference conditions, control sediments and toxicity thresholds for limnic sediment contact tests.     

Pressure-assisted ozonation of PCB and PAH contaminated sediments

Sediment contamination by recalcitrant organics such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) is prevalent and of a great concern. Remediation efforts are hampered by the hydrophobic nature of the contaminants that limits their availability as well as by the sediment matrix that limits their exposure to treatment agents. Using contaminated sediment samples from the Passaic River, St. Louis River, Waukegan Harbor, and Wells National Estuarine Research Reserve, this research demonstrated a new ozonation technique that incorporates rapid, successive cycles of pressurization (690 kPa) and depressurization, enabling more effective treatment than conventional ozonation would. Conventional ozonation reached maximum 60% and 40% removal of PAHs from the Passaic River (40 mg kg(-1) initially) and St. Louis River sediment (520 mg kg(-1) initially), respectively, in 1h; however, removals ceased despite prolonged treatment for 2h. The pressure-assisted technique removed 96% of PAHs from both river sediments within 1h; it completely removed both PAHs (16 mg kg(-1) initially) and PCBs (5.1 mg kg(-1) initially) from the Waukegan Harbor sediment in 0.5 h. The heightened treatment is explained by soil aggregate fracturing upon pressure cycles that exposes the contaminants as well as by the confluence of hydrophobic contaminants and O(3) at the gas-liquid interface in the presence of microbubbles. The technique is expected to accelerate O(3) treatment of a wide range of organic contaminants, and it may provide treatment to dredged and stored contaminated sediment.     

A mathematical algorithm to identify toxicity and prioritize pollutants in field sediments

In order to evaluate sediment toxicity, a mathematical algorithm was developed to compute the toxicity of multiple component mixtures acting in an additive manner. A statistical approach was devised to determine the presence of potential interactive effects among mixture components. The algorithm uses three kinds of data to obtain an integrative approach to sediment toxicity assessment: Microtox toxicity data (EC50 values), sediment pollutant concentration measurements, and sequential extraction (SEQ) data to investigate metal partitioning. To simplify the analysis of complex mixtures using a prioritization scheme based on intrinsic toxicity and relative abundance, a toxicity index (TI) was employed as an indicator of adverse ecological impact. In general, the ranking of contaminants using the TI approach was found to be most efficient in reducing computational time, and concentrations using bioavailability data from SEQ was found to be the best theoretical predictor of the experimental mixture toxicity value. Only a few pollutants that were present at the greatest abundance were needed to provide a good approximation of the calculated EC50 found when all components were included. Not only does this substantially reduce the computational time needed to determine the EC50, it could in some cases dramatically reduce the pollutant monitoring effort required to track toxicity effectively. This approach would have substantial implications for both risk assessment and for remediation strategies, making them more efficient by focusing on the priority pollutants identified.     

Potential impacts of water injection dredging on water quality and ecotoxicity in Limehouse Basin, River Thames, SE England, UK

The use of water injection dredging (WID) is increasing in the UK's inland waterways and marinas. Jets of water are injected under low pressure directly into bottom sediment creating a turbulent water-sediment mixture that flows under the influence of gravity. Many of these sediments are highly contaminated and little is known of the effects of contaminant release on water quality or the risk to biota living in both the sediment and the water column. Sediment cores were collected from Limehouse Basin, a proposed WID site in SE England and current sediment toxicity was assessed using a number of techniques. Comparison of metal data to US sediment quality guidelines indicated intermediate levels of toxicity while, calculation of acid volatile sulphide to simultaneously extracted metal ratios underestimated the potential toxicity to sediment dwelling organisms. In contrast, porewater ammonia concentrations were in excess of all published ecotoxicological guidelines and indicate serious risk to biota. Re-suspension experiments were used to mimic the effects of WID on overlying water quality and ecotoxicity tests were carried out on elutriates using Daphnia magna to examine the impacts on biota. Concentrations of a range of metals in the elutriates predict that adverse biological effects would be observed during WID, however only 10% of the elutriate samples caused an adverse effect on Daphnia. Limehouse Basin is a complex aquatic environment receiving predominantly fresh waters while the sediments have high porewater chloride concentrations reminiscent of previous tidal inputs to the basin, making the choice of test organism problematic.     

Occurrence of polybrominated diphenylethers, polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in coastal sediments from Spain

Fifteen sediment samples were analysed in order to determine their content of polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs). Samples were collected from several hot spots on the Spanish coast, such as the harbours of Almeria and Tarragona, and the mouths of the Besos and Llobregat rivers in Barcelona. A generic analytical procedure based on Soxhlet extraction followed by an automated cleanup system and gas chromatography-ion trap-mass spectrometry was employed for determining the toxic congeners of PCDDs and PCDFs, as well as dioxin-like PCBs. As regards PBDE determinations, a rapid method based on the use of selective pressurized liquid extraction followed by gas chromatography-negative ion chemical ionization-mass spectrometry was applied. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. WHO-TEQ values ranged from 0.3 to 75 pg/g dry weight (dw), with PCB contribution on the toxicity of the samples between 1 and 84%. Total PBDE levels ranged from 2.7 to 134 ng/g dw, with BDE-209 contribution on the total PBDE contamination between 50 and 99%.     

In-situ partitioning of butyltin compounds in estuarine sediments

The in-situ solid/pore-water partitioning of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was determined for an estuarine sediment profile collected from a commercial marina. Total butyltin levels exceeded sediment quality guideline values, and were 220-8750 microg/kg for TBT, 150-5450 microg/kg for DBT and 130-4250 microg/kg for MBT. Pore-water butyltin concentrations ranged from 0.05 to 2.35 microg/l for TBT, 0.07-3.25 microg/l for DBT, and 0.05-0.53 microg/l for MBT. The partitioning of butyltin compounds between the sediment solid-phase and pore-water was described by an organic carbon normalised distribution ratio (D(OC)). The observed D(OC) values were similar for TBT, DBT and MBT, and were 10(5)-10(6) l/kg. Values for the Butyltin Degradation Index (BDI) were larger than 1 at depths greater than 10 cm below the sediment/water-column interface. This indicates that substantial TBT degradation has occurred in the sediments, and suggests that natural attenuation may be a viable sediment remediation strategy.