Comparative evaluation of a bioluminescent bacterial assay in terrestrial ecotoxicity testing

Despite the widespread and successful use of luminescence-based bioassays in water testing, their applications to soils and sediments is less proven. In part this is because such bioassays have mainly been carried out in an aqueous-based medium and, as such, favour contaminants that are readily water-soluble. In this study, aqueous solutions and soils contaminated with heavy metals (HM), polar organic contaminants and hydrophobic organic contaminants (HOCs) were tested using a range of luminescence-based bioassays (Vibrio fischeri, Escherichia coli HB101 pUCD607 and Pseudomonas fluorescens 10586r pUCD607). For the first two chemical groups, the assays were highly reproducible when optimised extraction procedures were employed but for HOCs the bioassay response was poor. Quantitative structure-activity relationships (QSARs) obtained from aqueous solutions had a linear response although correlation for the chemicals tested using bacterial bioassays was significantly less sensitive than that of sublethal tests for Tetrahymena pyriformis. Bacterial and Dendrobaena veneta bioassay responses to extracts from HM amended soils showed that a clear relationship between trophic levels could be obtained. There is no doubt that the wide range of bioluminescent-based bioassays offers complementary applications to traditional testing techniques but there is a significant need to justify and optimise the extraction protocol prior to application.     

Estimating aquatic toxicity as determined through laboratory tests of great lakes sediments containing complex mixtures of environmental contaminants

We developed and evaluated a total toxic units modeling approach for predicting mean toxicity as measured in laboratory tests for Great Lakes sediments containing complex mixtures of environmental contaminants (e.g., polychlorinated biphenyls, polycyclic aromatic hydrocarbons, pesticides, chlorinated dioxins, and metals). The approach incorporates equilibrium partitioning and organic carbon control of bioavailability for organic contaminants and acid volatile sulfide (AVS) control for metals, and includes toxic equivalency for planar organic chemicals. A toxic unit is defined as the ratio of the estimated pore-water concentration of a contaminant to the chronic toxicity of that contaminant, as estimated by U.S. Environmental Protection Agency Ambient Water Quality Criteria (AWQC). The toxic unit models we developed assume complete additivity of contaminant effects, are completely mechanistic in form, and were evaluated without any a posteriori modification of either the models or the data from which the models were developed and against which they were tested. A linear relationship between total toxic units, which included toxicity attributable to both iron and un-ionized ammonia, accounted for about 88% of observed variability in mean toxicity; a quadratic relationship accounted for almost 94%. Exclusion of either bioavailability components (i.e., equilibrium partitioning control of organic contaminants and AVS control of metals) or iron from the model substantially decreased its ability to predict mean toxicity. A model based solely on un-ionized ammonia accounted for about 47% of the variability in mean toxicity. We found the toxic unit approach to be a viable method for assessing and ranking the relative potential toxicity of contaminated sediments.The U.S. Government right to retain a non-exclusive royalty free licence in and to any copyright is acknowledged.     

Comparison of PoraPak Rxn RP and XAD-2 adsorbents for monitoring dissolved hydrophobic organic contaminants

Accurate determination of the levels of dissolved hydrophobic organic contaminants (HOCs) is an important step in estimating the dynamics of their inputs and losses in aqueous systems. This study explores an alternative method for efficiently sampling dissolved HOCs while mitigating a number of sampling artifacts associated with traditional methods. The adsorption characteristics of a new polymeric resin, PoraPak Rxn RP (PPR), were assessed using sorption isotherm experiments and fixed bed adsorption studies. The adsorption capacities and breakthrough times for four model contaminants (phenol, p-nitrophenol, naphthalene, and 2,4,6-tribromophenol) were proportional to the contaminant’s hydrophobicity. The ability of PPR to isolate dissolved polychlorinated biphenyls (PCBs) in real samples was compared with that of XAD-2, a well-known macroporous polymer that suffers from high background contamination. The results indicated that the PPR resin can be effectively used for monitoring HOCs, with low ∑PCB levels in blanks, decreasing solvent use, and reducing extraction times.     

Assessment of phenanthrene bioavailability in aged and unaged soils by mild extraction

It has become apparent that the threat of an organic pollutant in soil is directly related to its bioavailable fraction and that the use of total contaminant concentrations as a measure of potential contaminant exposure to plants or soil organisms is inappropriate. In light of this, non-exhaustive extraction techniques are being investigated to assess their appropriateness in determining bioavailability. To find a suitable and rapid extraction method to predict phenanthrene bioavailability, multiple extraction techniques (i.e., mild hydroxypropyl-β-cyclodextrin (HPCD) and organic solvents extraction) were investigated in soil spiked to a range of phenanthrene levels (i.e., 1.12, 8.52, 73, 136, and 335 μg g^− 1 dry soil). The bioaccumulation of phenanthrene in earthworm (Eisenia fetida) was used as the reference system for bioavailability. Correlation results for phenanthrene suggested that mild HPCD extraction was a better method to predict bioavailability of phenanthrene in soil compared with organic solvents extraction. Aged (i.e., 150 days) and fresh (i.e., 0 day) soil samples were used to evaluate the extraction efficiency and the effect of soil contact time on the availability of phenanthrene. The percentage of phenanthrene accumulated by earthworms and percent recoveries by mild extractants changed significantly with aging time. Thus, aging significantly reduced the earthworm uptake and chemical extractability of phenanthrene. In general, among organic extractants, methanol showed recoveries comparable to those of mild HPCD for both aged and unaged soil matrices. Hence, this extractant can be suitable after HPCD to evaluate risk of contaminated soils.     

Integrative sediment assessment at Atlantic Spanish harbours by means of chemical and ecotoxicological tools

This study refers to the integrative assessment of sediment quality in three harbour areas at the Spanish Atlantic Coast: Vigo (Northwestern Spain), Bilbao and Pasajes (Northern Spain). At each site, two lines of evidence have been considered: chemical analyses (metal, PAH and PCB concentrations in sediments and ammonia concentration in bioassays) and toxicity tests (Microtox®, Corophium sp. marine amphipod and Paracentrotus lividus sea urchin larvae). Chemical and ecotoxicological results have been integrated by means of a tabular matrix and a multivariate factorial analysis (FA). Highly toxic samples have been characterised in Vigo and Pasajes harbours while Bilbao samples present toxicity levels ranging from non-toxic to moderately toxic. High toxicity is associated with high levels of contaminants whereas confounding factors (ammonia, organic matter and mud) have been identified to be the main cause of low to moderate toxicity. Based on the obtained results, it can be concluded that deriving potential toxicity of sediments based on comparison with Sediment Quality Guidelines (SQGs) is in agreement to toxicity results in areas presenting high levels of contaminants. However, at lower levels of toxicity (low to moderate), the mismatch between the potential toxicity (SQG approach) and the toxicity measured by bioassays is greater, as the former only accounts for chemical concentrations, without considering the interaction between contaminants and the effect of confounding factors. Contrarily, the multivariate analysis seems to be a robust tool for the integration and interpretation of different lines of evidence in areas affected by different sources of contamination.     

Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon

Determination of only total element in sediments does not give an accurate estimate of the likely environmental impacts. Speciation study of metals in sediment provides information on the potential availability of metals (toxic) to biota under various environmental conditions. In water, the toxic metal specie is the free hydrated metal ion. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on Qaraaoun Reservoir, Lebanon. Earlier studies focused only on total metal concentrations in sediment and water. The objective of this study was to determine metal speciation (Fe, Cr, Ni, Zn, Cu, Pb, Cd) in the (operationally defined) sediment chemical fractions and metal speciation in reservoir water. This would reflect on metal bioavailability and toxicity. Water samples and bed sediments were collected from nine sites during the dry season and a sequential chemical fraction scheme was applied to the <75-??m sieve sediment fraction. Metal content in each fraction was determined by the FAAS technique. The data showed that the highest percentages of total metal content in sediment fractions were for: Fe in residual followed by reducible, Cr and Ni in residual and in reducible, Cu in organic followed by exchangeable, Zn in residual and in organic, Pb in organic and carbonate, Cd was mainly in carbonate. Total metal content in water was determined by ICP-MS technique and aqueous metal speciation was predicted using AQUACHEM software interfaced to PHREEQC geochemical computer model. The water speciation data predicted that a high percentage of Pb and Ni were present as carbonate complex species and low percentages as free hydrated ions, highest percentage of Zn as carbonate complex species followed by free hydrated ion, highest percentage of Cd as free hydrated ion followed by carbonate complex species. The sensitivity attempt of free hydrated ion of Ni, Zn, Pb, and Cd in reservoir water revealed dependence of Zn and Cd on pH and alkalinity, while Ni and Pb were only dependent on pH.     

Injectors for capillary gas chromatography and their application to environmental analysis

The application of different injectors in capillary gas chromatography (GC) analysis of semi-volatile organic contaminants in environmental samples prepared in organic solvents is reviewed. The injectors examined include a split/splitless injector in splitless mode (SS), cold on-column (COC), and programmable temperature vaporizer (PTV) and adaptations of these injector designs. Key issues when selecting an injector include properties of the analyte, such as potential for thermal degradation or discrimination of high boiling point compounds within the injector, and the ability of the GC systems to handle large volume injections (LVI) primarily to lower detection limits and allow direct coupling with sample preparation techniques such as at-line or on-line solid phase extraction (SPE). LVI also require consideration of matrix interference issues. This review examines only injector chamber modifications that are feasible with a standard GC configuration, however some modifications to the chromatographic system to extend the range of applicability of gas chromatography analysis for environmental samples are also noted.     

Sediment quality triad assessment of an industrialized estuary of the northeastern USA

The lower Passaic River in northern New Jersey (USA) has been heavily industrialized since the mid-nineteenth century and its shoreline and aquatic habitats degraded or destroyed. Similar to other urban systems, Passaic River sediments, both surface and buried, historically have contained elevated levels of numerous contaminants that may pose risks to ecological receptors and humans. Sediments from 15 stations in the lower Passaic River and 3 reference stations in the Mullica River in southern New Jersey were sampled in 1999 and characterized for chemical contamination, toxicity, and impairment of the benthic community. The objective of this study was to determine the incidence, degree, and nature of degraded surficial sediments in the area to support subsequent plans for restoration of the system. Results demonstrated that Passaic River sediments had concentrations of many organic and inorganic contaminants at levels significantly greater than the reference area and effect-based guidelines. Sediments were toxic to marine amphipods at 11 stations and the benthic assemblages were impaired relative to the reference area at all stations. The weight-of-evidence of this sediment quality triad (SQT) assessment indicates that impacts from multiple contaminants are occurring throughout the lower Passaic River and, that these impacts must be evaluated further and addressed as part of ongoing restoration initiatives for the river.     

Metal Extraction from Road Sediment using Different Strength Reagents: Impact on Anthropogenic Contaminant Signals

Washoff of road deposited sediment into storm drainsystems is one of the major contributors to nonpoint sourcepollution in urban fluvial networks. These sediments contain avariety of potentially toxic organic and inorganic contaminants.Road sediment from 13 locations in an urban (non-industrialized)drainage basin, and soil from 10 background (control) locationswere collected to assess total and labile fractions of Al, Co,Cu, Fe, Mn, Ni, Pb and Zn. Four digestions, of varying strength,were used to assess contaminant levels, these included: a totalfour-acid digestion, a microwave-assisted digestion withconcentrated nitric acid (USEPA Method 3051), a 0.5 M `cold' HCl,and a 0.05 M EDTA (pH 7). Road sediment data indicate that Al,Co, Fe, Mn and Ni were primarily lithogenic in origin, while Cu,Pb and Zn showed very significant anthropogenic signals, mostprobably from vehicle-related sources. Median Pb concentrationenrichment ratios for the EDTA extraction were about 42,indicating an extreme anthropogenic signal. The weak extractants(HCl and EDTA) are considered in this study to be superior intheir ability to characterize the degree of anthropogeniccontamination and should be utilized more widely in environmentalcontaminant studies.     

Bacterial biosensors for rapid and effective monitoring of biodegradation of organic pollutants in wastewater effluents

Significant amounts of toxic substances which are hazardous to animals, plants, microorganisms, and other living organisms including humans are released annually into aquatic and terrestrial environments, mostly from improper wastewater discharges. Early detection of such pollutants in wastewater effluents and proper monitoring before their final release into the environment is therefore necessary. In this study, two whole-cell bacterial biosensors were constructed by transforming competent cells of Shigella flexneri and Shigella sonnei with pLUX plasmids and evaluated for their potential to monitor wastewater samples undergoing degradation by measuring bioluminescence response using a microplate luminometer. Both bacterial biosensors were found to be extremely sensitive to the wastewater samples, with different patterns, concomitant with those of the COD removals demonstrated at the different days of the degradation. Generally higher bioluminescence values were obtained at the later days of the degradation period compared to the initial values, with up to 571.76% increase in bioluminescence value obtained at day 5 for 0.1% (v/v) effluent concentration. Also, a steady decrease in bioluminescence was observed for the bacterial biosensors with increasing time of exposure to the wastewater effluent for all the sampling days. These biosensor constructs could therefore be applicable to indicate the bioavailability of pollutants in a way that chemical analysis cannot, and for in situ monitoring of biodegradation. This has great potential to offer a risk assessment strategy in predicting the level of bioremediation required during municipal wastewater treatment before their final discharge into the aquatic milieu.     

Chemical contamination assessment of Gulf of Mexico oysters in response to hurricanes Katrina and Rita

Hurricane Katrina made landfall on August 29, 2005 and caused widespread devastation along the central Gulf Coast states. Less than a month later Hurricane Rita followed a similar track slightly west of Katrina’s. A coordinated multi-agency response followed to collect water, sediment and tissue samples for a variety of chemical, biological and toxicological indicators. The National Oceanic and Atmospheric Administration’s National Status and Trends Program (NS&T) participated in this effort by measuring chemical contamination in sediment and oyster tissue as part of the Mussel Watch Program, a long-term monitoring program to assess spatial and temporal trends in a wide range of coastal pollutants. This paper describes results for contaminants measured in oyster tissue collected between September 29 and October 10, 2005 and discusses the results in the context of Mussel Watch and its 20-year record of chemical contamination in the region and the nation. In general, levels of metals in oyster tissue were higher then pre- hurricane levels while organic contaminants were at or near record lows. No contaminant reported here exceeded the FDA action level for food safety.     

Characterization of organic chemical contaminants in sediments from Jobos Bay, Puerto Rico

Jobos Bay, located on the southeastern coast of Puerto Rico, contains a variety of habitats including mangroves, seagrass meadows, and coral reefs. The watershed surrounding the bay includes a number of towns, agricultural areas, and the Jobos Bay National Estuarine Research Reserve (NERR). Jobos Bay and the surrounding watershed are part of a Conservation Effects Assessment Project (CEAP), involving the Jobos Bay NERR, the US Department of Agriculture, and the National Oceanic and Atmospheric Administration (NOAA) to assess the benefits of agricultural best management practices (BMPs) on the terrestrial and marine environments. As part of the Jobos Bay CEAP, NOAA collected sediment samples in May 2008 to characterize over 130 organic chemical contaminants. This paper presents the results of the organic contaminant analysis. The organic contaminants detected in the sediments included polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and the pesticide DDT. PAHs at one site in the inner bay near a boat yard were significantly elevated; however, all organic contaminant classes measured were below NOAA sediment quality guidelines that would have indicated that impacts were likely. The results of this work provide an important baseline assessment of the marine environment that will assist in understanding the benefits of implementing BMPs on water quality in Jobos Bay.     

Distribution and speciation of selected metals in surface sediments, from the tropical Zuari estuary, central west coast of India

Estuarine sediments are major reservoirs for the metals. Distribution and mobility of metals within estuaries depends strongly on their specific chemical form. In the present study, surface sediments from Zuari estuary, Goa were analysed by a sequential procedure for Fe, Mn, Cu, Zn, Cr and Co to determine their distribution in five geochemical phases (Exchangeable, carbonate, Fe-Mn oxide (reducible) organic bound (oxidisable) and residual). The total metal content, sand, silt, clay and organic carbon were also determined of the surface sediments. The total metal contents were found to be greater than the background concentrations of average shale values as well as to that of earlier studies indicating enrichment probably due to the anthropogenic origin of metals. The results obtained from sequential procedure showed that among the studied elements, Mn and Co are potentially available in the bioavailable fractions (exchangeable, carbonate and Fe-Mn oxide bound fractions) indicating their importance in toxicity whereas rest of the metals viz. Fe, Cu, Zn and to some extent Cr are largely available in residual phase although they are available in other fractions. The main source of metals to the estuary is mining and its associated activities in the study area. Chemical speciation by sequential extraction procedure has helped in assessing the mobility, bioavailability, diagenesis and toxicity of metals and hence giving a better insight into the ultimate fate of pollutants, which are introduced into the estuarine environment. To understand the risk of the metals to the sediment dwelling organisms the data were compared with the Sediment Quality Values (SQV) using SQUIRT. Also, correlation and Factor analysis were carried out to understand the associations of metals in the different fractions with sand, silt, clay, organic carbon and with other metals.     

Phosphorous speciation in surface sediments of the Cochin estuary

Sequential chemical extraction using chelating agents were used to study the P dynamics and its bioavailability along the surface sediments of the Cochin estuary (southwest coast of India). Sediments were analyzed for major P species (iron bound P, calcium bound P, acid soluble organic P, alkali soluble organic P and residual organic P), Fe, Ca, total carbon, organic carbon, total nitrogen and total sulfur contents. An abrupt increase in the concentration of dissolved inorganic P with increasing salinity was observed in the study region. Iron-bound P exhibited a distinct seasonal pattern with maximum values in the monsoon season when fresh water condition was prevailed in the estuary. As salinity increased, the percentage of iron-bound P decreased, while that of calcium-bound P and total sedimentary sulfur increased. C/P and N/P ratios were low which indicate that large amounts of organic matter enriched with P tend to accumulate in surface sediments. The high organic P contribution in the sedimentary P pool may indicate high organic matter load with incomplete mineralization, as well as comparatively greater percentage of humic substance and resistant organic compounds. Principal component analysis is employed to find the possible processes influencing the speciation of P in the study region and indicate the following processes: (1) the spatial and seasonal variations of calcium bound P and acid soluble organic P was mainly controlled by sediment texture and organic carbon content, (2) sediment redox conditions control the distribution of iron bound P and (3) the terrigenous input of organic P is a significant processes controlling total P content in surface sediments. The bioavailable P was very high in the surface sediments which on an average accounts for 59 % in the pre-monsoon, 65 % in the monsoon and 53 % in the post-monsoon seasons. The surface sediments act as a potential internal source of P in the Cochin estuary.     

Chemometric application in identifying sources of organic contaminants in Langat river basin

Increasing urbanization and changes in land use in Langat river basin lead to adverse impacts on the environment compartment. One of the major challenges is in identifying sources of organic contaminants. This study presented the application of selected chemometric techniques: cluster analysis (CA), discriminant analysis (DA), and principal component analysis (PCA) to classify the pollution sources in Langat river basin based on the analysis of water and sediment samples collected from 24 stations, monitored for 14 organic contaminants from polycyclic aromatic hydrocarbons (PAHs), sterols, and pesticides groups. The CA and DA enabled to group 24 monitoring sites into three groups of pollution source (industry and urban socioeconomic, agricultural activity, and urban/domestic sewage) with five major discriminating variables: naphthalene, pyrene, benzo[a]pyrene, coprostanol, and cholesterol. PCA analysis, applied to water data sets, resulted in four latent factors explaining 79.0% of the total variance while sediment samples gave five latent factors with 77.6% explained variance. The varifactors (VFs) obtained from PCA indicated that sterols (coprostanol, cholesterol, stigmasterol, β-sitosterol, and stigmastanol) are strongly correlated to domestic and urban sewage, PAHs (naphthalene, acenaphthene, pyrene, benzo[a]anthracene, and benzo[a]pyrene) from industrial and urban activities and chlorpyrifos correlated to samples nearby agricultural sites. The results demonstrated that chemometric techniques can be used for rapid assessment of water and sediment contaminations.     

Heavy metals in the fishery products of low Lazio and the use of metallothionein as a biomarker of contamination

This study aims to investigate the use of metallothionein as a biomarker and its environmental impact on aquatic systems. According to the species’ characteristics, the interactions of toxic elements with living organisms in marine water can lead to biomagnifications in the trophic chain or bioconcentration of what is in the water. In many aquatic organisms, the presence of metallothionein proteins was studied. The chemical analysis of these bioindicators establishes, therefore, a sensitive method for the measurement of bioavailability which, over the years, allows for the quantification of the current pollution agents in the environment. Two study areas were selected along the Latium coasts. They are differentiated by their economic activities and their kind and level of environmental impact (mainly on marine pollution). These areas were selected in order to differentiate the maximum degree of both economic development and environmental quality. In particular, the presence of pollutants in the sea due to land activities was evaluated to compare the quality of the fishing products obtained from locations subject to various environmental impacts. The heavy metal concentrations were evaluated in water samples taken from different 30 sections of the fishes in order to understand the metabolism and origin of these contaminants. The primary metals studied were: mercury (Hg), zinc (Zn), nickel (Ni), lead (Pb), cadmium (Cd), and copper (Cu). All data produced were analyzed via multivariate analyses in order to provide a final and reliable indicator.     

Freshwater leeches (Hirudinea) as a screening tool for detecting organic contaminants in the environment

In earlier work, we found that leeches from an industrially polluted creek bioaccumulated chlorophenols to much higher concentrations than other resident benthic invertebrates and fish. We suggested that leeches may have significant potential as biomonitors for these and other organic contaminants in the environment. In this study, we compared the bioaccumulation and depuration of 16 organic compounds, including eight chlorophenols (CPs), lindane, DDT and four derivatives, benzothiazole (BT) and 2-(Methylthio)benzothiazole (MMBT) for three species of leeches. Dina dubia had the highest bioaccumulation capacity for most contaminants, but residues persisted longest in Erpobdella punctata. Helobdella stagnalis appeared capable of degrading some compounds. Half lives of CPs, DDT and DDT derivatives were generally longer than one month. In contrast, half lives were only 1 day for lindane, 1–2.5 days for MMBT and 7 days for BT despite very high initial tissue concentrations of the latter two compounds. Bioconcentration factors for contaminants in leeches were higher than those reported for other aquatic organisms. Half lives for lindane, DDT and DDT derivatives were consistent with the literature for other organisms, but half lives for CPs were much longer. The results suggest that leeches would be excellent biomonitors of both continuous and intermittent contamination of a waterway with CPs and DDT, as they retain these compounds for long periods after exposure. Their usefulness as a screening tool for lindane and benzothiazoles would be limited to chronically contaminated environments.     

Distribution and chemical partitioning of heavy metals in marine near-shore sediment cores: a case study from the Xugou, Lianyungang, China

The concentrations and chemical partitioning of heavy metals (Co, Cr, Ni, Zn, Cu, and Pb) in the marine near-shore sediment cores were investigated. Typically, the mean concentrations from Core B sediment samples were 98.6, 21.1, 47.0, 46.4, 107.6, and 31.9 mg kg^???1 for Cr, Co, Ni, Cu, Zn, and Pb, respectively. The heavy metal concentrations were normalized to commonly used reference elements Al, Li, Sc, and total organic carbon. Based on Pearson coefficients, Li was found to be a good normalizer for Co (r?= 0.974), Cr (r?= 0.967), Ni (r?= 0.898), and Zn (r?= 0.929) in 80 sediment samples from three sampling sites. However, the correlation coefficients between Li and Cu, and Li and Pb were relatively low. Multivariate statistic approaches (Principal Component Analysis and Cluster Analysis) were adopted for data treatment, allowing the identification of two main factors controlling the heavy metal variability in the sediments. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. The results showed that the residual, Fe/Mn oxides and Organic/sulfide fractions were dominant geochemical phases in the enriched sections, indicating low bioavailability of heavy metals in sediments.     

电线电缆行业漆包线生产工艺废气中有机物的GC/MS测定

本文以活性炭、ＴｅｎａｘＧＣ、聚氨酯泡沫为吸附材料,用二硫化碳洗脱、二氯甲烷提取、加热解吸三种脱附方式,并以色谱／质谱（ＧＣ／ＭＳ）联用仪为测试手段,对漆包线生产工艺废气中的有机物进行了测定,共检出７２种有机化合物。本文进行了不同采集方式间的比较,提出了电线电缆行业工艺废气中有机化合物的系统分析方法。     

Solid-phase microextraction to monitor the sonochemical degradation of polycyclic aromatic hydrocarbons in water

Solid-phase microextraction (SPME) coupled with GC-MS has been used to monitor the degradation of polycyclic aromatic hydrocarbons (PAHs) by ultrasound treatment. Immersion SPME sampling enabled the fast and solventless extraction of target contaminants at the low microg l(-1) concentration level. The developed protocol was found to be linear in the concentration range from 0.1 to 50 microg l(-1) for most target analytes, with the limits of detection ranging between 0.01 and 0.70 microg l(-1) and the relative standard deviations between 4.31 and 27%. The developed SPME protocol was used to follow concentration profiles of aqueous solutions containing 16 PAHs, which were subject to low frequency ultrasonic irradiation. At the conditions employed in this study (80 kHz of ultrasound frequency, 130 W l(-1) of applied electric power density, 30 microg l(-1) of initial concentration for each of the 16 PAHs), sonochemical treatment was found capable of destroying the lower molecular weight PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) within 120-180 min of irradiation. The higher molecular weight PAHs were more recalcitrant to ultrasound treatment.