Oil Spill Simulation and Validation in the Arabian (Persian) Gulf with Special Reference to the UAE Coast

The use of numerical modeling in oil spill incidents is a well established technique that has proven to provide cost-effective and reasonable estimates of oil surface drift. Good predictability of such models depends highly on the quality of the input data of the incident and on the model calibration effort. This paper presents the results of simulating oil spillage trajectory in the Arabian (Persian) Gulf. The study employed a 3-D rectilinear hydrodynamic model combined with oil spill model. Typical representative environmental conditions of the Arabian Gulf were first setup into a hydrodynamic circulation model using data from various sources. The performance of the hydrodynamic model was then tested against measurements of tidal fluctuation and sea currents at selected locations. The spill analysis model was setup using the flow field produced from the hydrodynamic simulation and its performance was further validated against documented events of Al-Ahmadi historical oil spill crisis in the Gulf. The comparison of the actual and simulated oil spill drift was found reasonably acceptable allowing for further application in risk assessment studies in UAE Coastal water and in the entire Arabian Gulf as well.     

Evaluating soluble toxicants in contaminated soils

Complex mixtures of water soluble materials from contaminated soils can move into groundwater and surface water by leaching, percolation, and runoff. We evaluated the potential toxicity of leachable materials from seven soils. Five soil samples were obtained at designated toxic or hazardous waste sites, and two additional soils samples were obtained from a coal storage area and from an agricultural field. Acidified tap water (pH 4.5) was used to extract toxic materials from elution columns filled with soil samples. Extracts were used as complex mixtures to conduct acute toxicity tests using Daphnia and chronic effects tests using aquatic microcosms. Three classes of effects were observed. Three soil leachates showed acute and chronic toxicity at less than 3% leachate. Two of these soils were contaminated by materials used in wood preserving, and the third soil was contaminated with heavy metals and acid. Two soils showed moderate acute toxicity but no chronic toxicity in microcosm tests. One of these soils was contaminated with low levels of chromium while the other soil was from a coal storage area. The remaining two soil samples showed no toxicity in either acute or chronic toxicity tests. One of these soils was from a reference agricultural field while the other soil was contaminated with solvents. The failure to detect toxicity in the solvent contaminated sample was attributed to the hydrophobicity of the toxicity materials. Results of these toxic screenings are in the same range as leachate toxicities estimated using other methods, although other methods use extraction materials that may interfere with some biological tests. Toxicological evaluations of materials from suspected contaminated soil are recommended for prioritizing clean up efforts at waste sites and for determining if toxic materials and contaminated soils have been effectively removed.     

Seawater causes rapid trace metal mobilisation in coastal lowland acid sulfate soils: Implications of sea level rise for water quality

Coastal floodplains are highly vulnerable to inundation with saline water and the likelihood of inundation will increase with sea level rise. Sediment samples from floodplains containing coastal lowland acid sulfate soils (CLASS) in eastern Australia were subjected to increasing seawater concentration to examine the probable effects of sea level rise on acidity and metal desorption. Ten soils were mixed with synthetic seawater concentrations varying from 0% to 100% at a solid:solution ratio of 1:10 for 4 h. There was a slight decrease in pH (≈ 0.5 units) with increasing seawater concentration following treatment, yet, calculated acidity increased significantly. In most soil treatments, Al was the dominant component of the calculated acidity pool. Al dominated the exchange complex in the CLASS and, correspondingly, was the major metal ion desorbed. In general, concentrations of soluble and exchangeable Al, Fe²⁺, Ni, Mn and Zn in all soil extracts increased with increasing salinity. Increasing trace metal concentrations with increasing seawater concentration is attributed to the combined effects of exchange processes and acidity. The increasing ionic strength of the seawater treatments displaces trace metals and protons adsorbed on sediments, causing an initial decrease in pH. Hydrolysis of desorbed acidic metal cations can further contribute to acidity and increase mobilisation of trace metals. These findings imply that saline inundation of CLASS environments, even by relatively brackish water may cause rapid, shorter-term water quality changes and a pulse release of acidity due to desorption of acidic metal cations.     

Toxicity reduction of Ontario hydro radioactive liquid waste

The radioactive liquid waste (RLW) system in Ontario Hydro's pressurised heavy water reactors collects drainage from a variety of sources ranging from floor drains to laundry waste. RLW effluent was intermittently toxic to rainbow trout andDaphnia magna during the first phase of Ontario's Municipal Industrial Strategy for Abatement (MISA) Program, apparently as a result of the interaction of a variety of known and unknown organic and inorganic compounds. Accordingly, we employed a tmatment-based approach to reducing its toxicity, supplemented by chemical analysis. Two series of toxicity reduction tests were conducted. The fast series explored the potential for sorption of the possible toxicants, while the accord series incorporated a wider variety of treatments. Of the 24 samples in the first test series, 17 were toxic (D. magna mortality ≥ 50%). Of the toxic samples, only 7 of 17 were still toxic after passage through an activated carbon column, but 5 of 6 samples tested remained toxic after passage through a metal chelating resin column. In the second series, at least one of the treatments was effective in reducing toxicity of all samples which were initially toxic (16 of 24 samples), but no one treatment was effective for all toxic samples. Three treatments (UV/H₂O₂ photo-oxidation with prior pH adjustment, or passage through a column of either a non-functioalized (N-F) resin or a mixture of N-F resin and a weak base (W-B) anion exchange rain), were effective in reducing the toxicity of more than 50% of the toxic samples; yet roughly 25% of these samples remained toxic after treatment O₂ sparging, UV/H₂O₂ photo-oxidation without prior pH adjustment, and passage through a column of the W-B Resin were less effective, as more than 50% of the samples remained toxic after treatment. Filtering was not effective, as all of the treated samples (9/9) retained their toxicity. There was no obvious correspondence between toxicity and the concentrations of metals (Cu, Zn, Fe, Al and Cd) nor were any simple relationships apparent between toxicity and Total Organic Carbon or NH₃ concentrations. At stations where radioactive liquid wastes are segregated, toxicity was also segregated, suggesting that we may be able to address the problem at source through a combination of Best Management Practices and smaller scale treatment facilities.     

Reduction in the Acute Toxicity of Explosive Wastewater Containing Toxic Nitroaromatic Compounds by a Nanoscale Zerovalent Iron Pretreatment Process

The feasibility of using nanoscale zerovalent iron (nZVI) treatment for reducing the acute toxicity of explosive wastewater, such as 2,4,6-trinitrotoluene (TNT) red water which contains highly toxic nitroaromatic compounds (NACs), has been investigated. The water quality was evaluated before and after nZVI treatment using several different analytical techniques, including UV?CVis spectroscopy, X-ray photoelectron spectroscopy, high-performance liquid chromatography, and gas chromatography/mass spectroscopy. The acute toxicity of the wastewater was tested using a luminescence bacterium bioarray. The results indicated that the most significant toxic NACs, such as dinitrotoluene sulfonates, had been effectively removed from the TNT red water by nZVI together with the small amounts of other NACs. Following 1?h of the nZVI processing treatment, the acute toxicity of the TNT wastewater was reduced by approximately 94?%. This treatment would therefore be useful for the pretreatment of wastewaters prior to the application of a biological process. The reduction in the biotoxicity of the wastewater was based on the reductive conversion processes and adsorption behaviors of nZVI.     

Polycyclic Aromatic Hydrocarbons in Seawater, Sediment, and Rock Oyster Saccostrea cucullata from the Northern Part of the Persian Gulf (Bushehr Province)

The concentration of polycyclic aromatic hydrocarbons (PAHs) was determined in seawater, sediment, and Rock oyster Saccostrea cucullata collected from four sampling sites in the inter-tidal areas of Bushehr province. The total concentrations of 14 PAHs varied from 1.5 to 3.6 ng/L in seawater, 41.7 to 227.5 ng/g dry weight in surface sediment, and 126 to 226.1 ng/g dry weight in oyster tissue. In comparing PAH concentrations among the three matrices in Bushehr province, data showed that the pattern of individual PAHs in seawater, oyster, and sediment were different. The oysters tended to accumulate the lower molecular weight and the more water-soluble PAHs. Sediment samples were distinguished from the sea water and oyster samples by the presence of high molecular weight PAHs, especially six-ring PAHs. Three- and four-ring PAHs were the most abundant compounds among the 14 PAHs investigated in surface seawater, sediment, and oyster samples. As expected, differences in octanol/water partition coefficient among individual PAHs and the greater persistence of the higher molecular weight PAHs contributed to the accumulation patterns in oyster and sediment. The results of the study suggested that the main sources of PAHs in the seawater and sediment in the region were mixed pyrolitic and petrogenic inputs.     

Distribution of Zn, Cd, Pb and Cu Metals in Groundwater of the Guadiamar River Basin

Traditionally, the Guadiamar River Basin (Seville, SouthwestSpain) has received pollution from two different sources. Inits upper course, from a pyrite exploitation and, in itslower reaches, from untreated urban and industrial wastes aswell as wastes from intensive agricultural activity. In 1998,the accidental release in the river of about 6 million m³ of acid water and sludge from mine tailings contributedto worsen the pollution of an already contaminated area. Themain polluting agents of the spill were heavy metals. Itaffected a large number of wells either directly or as a consequence of infiltration from polluted soils. Assessment of the pollution by total metal determination does not revealthe true environmental impact of the spill and speciation studies showing the distribution of the main pollutants are required. There is a direct association between the physicochemical speciation of an element and its bioavailability, toxicity and mobility. This article describesa distribution study of the metals Zn, Cd, Pb and Cu by speciation analysis of groundwater in six wells of the GuadiamarRiver Basin; the samples were taken several weeks after the spill. The speciation analysis resulted in the definition ofthree species categories: a) labile metal (H⁺ exchangeable),b) metal strongly associated to dissolved organic matter and c) metal associated with suspended material. Analysis was carried out by anodic stripping voltammetry (ASV). Metal speciation ingroundwater of the Guadiamar River Basin allows a differentiationbetween: on the one hand, metals from the mining spill, andon the other hand a less recent pollution from accumulatedinfiltration of either mining or agricultural origin, the last one due to an abuse of phytosanitary products.     

Metolachlor photodegradation study in aqueous media under natural and simulated solar irradiation

To elucidate the photochemical behavior of pesticide metolachlor, degradation was carried out in aqueous media of different compositions such as sea, river, lake, and distilled water under natural and simulated solar irradiation. In addition, the effect of important constituents of natural water such as dissolved organic matter (DOM, isolated from Pamvotis Lake) and nitrate ions was also examined. It was found that photodegradation proceeds via a pseudo-first-order reaction in all cases. The presence of DOM inhibits the photolysis reaction with half-lives ranging from 87 to 693 h whereas the degradation rate was accelerated up to 11 times in the presence of NO(3)(-). In addition, the toxicity of the degradation products formed (generally through hydroxylation, dealkylation, and cyclization reactions) was also performed using the marine luminescent bacterium Vibrio fisheri. Our results indicated a toxicity increase of the irradiated solution showing that photoproducts of higher acute toxic effects were formed.     

Sediment toxicity and heavy metals in eleven lime reference lakes of Sweden

Sediments from an eutrophic reference lake (L. HjÄlmaren) and eleven oligotrophic Swedish lakes were analyzed for heavy metals (Cd, Cr, Cu, Hg, Ni, Pb, and Zn) and tested for whole sediment toxicity to Daphnia magna. Whole sediment toxicity, expressed as 48-hr EC50 on a wet weight basis in reconstituted dilution water, ranged from 2.8% (most toxic) to >32% (least toxic). Correlations between bulk sediment heavy metal concentrations and toxicity were significant (P≤0.05) for Hg, Pb, and Zn. However, a causal connection between the concentrations of these metals and toxicity was not supported by the results from metal-spiked sediment toxicity tests. In addition sediment toxicity was not affected by the addition of EDTA, which is a strong chelator known to reduce metal toxicity. After storage for several months test sediments either remained nontoxic, toxic, or increased in toxicity. These results illustrate some of the difficulties in the interpretation of bulk sediment chemistry data and the release of toxic chemicals from sediment samples, highlighting the effect of sediment storage on toxicity.     

Comparison ofDaphnia magna,rainbow trout and bacterial-based toxicity tests of Ontario Hydro aquatic effluents

Over a one year program of intensive monitoring of effluents from Ontario Hydro's nuclear, fossil and hydroelectric generating facilities, theDaphnia magna and rainbow trout,Oncorhynchus mykiss, acute toxicity tests correlated well, with 61 % of the toxic effluents toxic to both species. If the effluent was toxic to only one of the test species it was generally toxic toD. magna, with from 23 to 57% of the toxic effluents toxic toD. magna only. The greater sensitivity ofD. magna to boiler blowdown effluent likely resulted from a combination of the low conductivity of boiler blowdown effluent and the smaller size and greater surface to volume ratio ofD. magna relative to rainbow trout.D. magna were also particularly susceptible to oil/water separator samples, with the daphnids frequently observed to be caught at the surface/water interface. These observations suggest that an accumulation of organic material at the air/water interface was responsible for the mortality ofD. magna. In subsequent tests, we also examined the relationship between theD. magna acute toxicity test and a bacterial-based assay (Toxi-Chromotest®) for several toxic effluents from Ontario Hydro stations to determine if bacterial-based tests could provide similar information in less time with smaller sample volumes. TheD. magma acute toxicity test did not correlate well with the bacterial-based Toxi-chromotest®. In particular, many of the samples which were toxic toD. magna were not toxic to the Toxi-chromotest® assay. The poor correlation between theD. magna and Toxi-chromotese® likely relates to both the relatively low toxicity of many of the effluent samples, and the fact that in many cases toxicity likely resulted from relatively simple combinations of inorganic toxicants. Accordingly, the Toxi-Chromotest® assay would not seem suitable as a surrogate for theD. magna acute toxicity test for our effluents.     

Ecotoxic impact of suspended solids collected from polluted surface waters

Scope and background

Earlier studies showed that artificially contaminated particulate matter could be responsible for acute effects in water fleas and fish. Physical/chemical measurements on suspended solids and river water collected in the field showed that these samples were often contaminated with mixtures of toxic molecules.

Objectives

The present pilot study was started to investigate the possible ecotoxic impact of suspended solids collected in situ.

Methods

Suspended solids and river waters were collected from 22 locations of polluted rivers in the Flanders. An extensive list of chemical components and physical parameters were measured in these matrices. Partition coefficients for water column and suspended solids were calculated. Toxicity of suspensions of solid materials was investigated in 3 test organisms of different trophic levels: Bacteria (BIOMET®), filter feeder (Daphnia magna) and fish (rainbow trout (Oncor-hynchus mykiss) or zebrafish (Danio rerio)). The acute toxicity was measured in a worst-case scenario using high concentrations of solids resuspended in standard medium and at standard conditions.

Results and discussion

The partition coefficients were highly variable, showing that this parameter is not simply related to the octanol/water partition coefficient or to the total organic carbon content of the solids in field conditions, as is often assumed in exposure models. The field material of some locations was toxic. Bacteria were the most sensitive test organisms, showing EC20 values at field relevant concentrations. For some samples, acute toxic effects were seen in fish and water fleas. The chemical content of the samples was very complex and could not simply be related to toxicity. Some samples were highly contaminated with toxic chemicals and yet caused no toxic effects, while other samples did not show extremely high concentrations, but were toxic to the test organisms.

Conclusions

Results show that biotests are needed, next to chemical measurements, to estimate the toxic impact of complex environmental matrices. A better understanding of the adsorption/desorption behaviour of toxic molecules in the water compartment and in living organisms will contribute to a better environmental risk assessment.

Recommendations and outlook

The results indicate that the ecotoxic impact of suspended solids in the field should be further investigated in realistic (non-worst-case) conditions, i.e. for chronic effects at field relevant concentrations. And more extensive scientific research is needed to understand the adsorption/desorption behaviour of toxic molecules in different physicochemical matrices.     

The Effect of Salinity on Tire Leachate Toxicity

Previous whole animal bioassays with scrap tireleachates demonstrated an antagonistic interactionbetween salinity and toxicity, but it is unknown ifthe effect is due to an interaction between saltsand toxic mode of action, or release of toxicantsfrom the rubber matrix. Microtox® bacterialluminescence bioassays were performed on tireleachate solutions in a gradient of salinities from0 to 25 ppt to assess salt/toxicant interactions.Leachate solutions generated at specific salinitieswere amended to higher salinities to assess theeffect of sea salt on toxicity vsleachability/solubility of toxicants. Salineleachate solutions were also diluted with freshwaterleachate. Original leachates and samples amendedwith additional salt were aged for 8 days andretested to assess longer term interactions betweensalt and toxicants. The toxicity of leachatesdecreased with increasing salinity up to 15 ppt,with no significant change at higher salinities.Adding sea salt to leachate solutions did notimmediately decrease toxicity significantly, exceptfor samples starting at zero salinity. This wasinterpreted as an indication of interaction betweensea salt and the toxic constituent(s) in theleachate. Salinity decreases also indicated a directeffect of sea salt on toxicants. Ageing samplesindicated a long term interaction between sea saltand leachate toxicants, but not degradation, over atleast a two week period. Tire leachates are probablya greater threat to freshwater habitats thanbrackish or marine habitats, but bioaccumulation ofpersistent organic contaminants from tires is an unknown.     

Species diversity and water quality in Galveston bay,Texas

The relationships between species diversity of phytoplankton, zooplankton, nekton and benthos samples and the water quality of Galveston Bay, Texas were quantitatively compared. Two water quality parameters (i.e., percent waste water or the toxicity of the water at a given sampling station) were found to be inversely correlated with species diversity. A computerized dispersion model was used to calculate percent waste water. Toxicity was measured by subjecting a blue-green alga (Coccochloris elebans) to water samples and by utilizing growth depression as the toxicity criterion. Waters from the Houston Ship Channel and the Trinity River were found to be significantly toxic and the dispersion model was again used to determine the distribution of toxicity to each bay area. Evidence that toxicity was dispersed with input waters was experimentally verified. Those areas receiving the greatest amounts of toxic effluent exhibited the lowest mean annual diversities. Predictive equations were generated, indicating that diversity at any point in the bay can be computed from Houston Ship Channel diversity and the dispersion model. Computations were also accomplished whereby dilution and/or treatment of waste inflows could be estimated to achieve a desired and/or acceptable diversity level in the bay.     

Domestic Sewage and Oil Spills in Streams: Effects on Edaphic Invertebrates in Flooded Forest, Manaus, Amazonas, Brazil

The influence of the aquatic environment on the terrestrial environment in areas subject to natural seasonal flooding has been little studied; especially lacking are studies that include anthropogenic impacts on these areas. Soil samples (including a superficial layer of litter) were collected between September 2000 and May 2001 on the banks of three streams in Manaus, Amazonas, Brazil in four seasons of the year, as determined by the flood pulse of the Rio Negro. The objectives of this study were to verify how an oil spill and urban sewage affect the abundance and richness of edaphic invertebrates on the stream banks and if these forms of pollution also influence the effect of the flood pulse on the natural community. Our results suggest reductions in the abundance and richness of edaphic invertebrates in the impacted areas and changes in the composition of edaphic invertebrate communities show a disturbance gradient from the banks of the unimpacted stream (Cristalino) to the banks of the stream that was impacted by the oil spill (Cururu), with more similar patterns occurring in impacted streams. The streams also showed effects of the flood pulse. Acarina, Entomobryidae, Formicidae, Staphylinidae and Carabidae were the only taxa that occurred in all three of the areas studied and in all of the sampling periods.     

Nitrogen and Phosphorus Flows in the Finnish Agricultural and Forest Sectors, 1910–2000

An assessment of the environmental quality of sediments at several locations of the Ría de Pontevedra (NW of Spain) was performed by integrating toxicity data obtained from multiespecies bioassays, chemical data from analysis of mussels and sediment, and physical–chemical parameters of the sampled sites. Subsequently, a toxicity identification evaluation (TIE) method intended for characterization and identification of the toxic agents was applied to the most polluted location by using the Paracentrotus lividus sea urchin bioassay. Both metals and organic compounds seem to be the causative agents of toxicity in elutriates of the studied sediment. Finally, multivariate statistics were applied for a better interpretation of results. A factor analysis was developed to establish the relationship among variables and to derive local sediment quality guidelines (SQG) by linking chemical contamination to biological effects. When multidimensional scaling and cluster analysis were performed to group the locations according to either the chemistry or toxicity data, P3-site was always clearly broken up the others. The different approaches all supported the same conclusion: site P3 can be considered highly contaminated by both trace metals and PAHs resulting in high toxicity for all the tested species.     

Dietary toxicity of decomposed arborescent leaf litter against larval mosquito: involvement of a lignin-polypeptidic complex

To characterize the toxic compounds involved in the dietary toxicity of decomposed arborescent leaf litter against larval mosquito, a toxic fraction was extracted from crude leaf litter by using hot water. Preliminary characterization of this fraction, called the insoluble fraction (IF) because it progressively precipitates after extraction, has suggested the involvement of lignin-like compounds in the toxicity. Further analyzes are currently being performed by using additional phytotoxicity-based methods. The involvement of lignin-like compounds in the toxicity was indicated by both the comparative effects of different enzymatic oxidative treatments and reversed-phase high-performance liquid chromatography analysis of the phenolic aldehydes and acids obtained after alkaline nitrobenzene oxidation. However, these lignin-like compounds may not be involved alone in the toxicity, as no specific feature of those components was associated with the toxicity. Among the possible compounds associated with lignin-like compounds in the toxicity, peptidic compounds were suggested by comparative determination of the C/N ratio and then revealed by denaturation experiments, use of specific binding protein molecules, and thin-layer chromatography analysis. A possible role of these peptidic compounds associated with lignin-like compounds in the dietary toxicity of the leaf litter against the larval mosquito midgut is discussed.     

Transformation of soil and plant cover contaminated with oil and salt water in the middle Ob’ river basin

Changes in the soil and plant cover caused by contamination with oil and salt water in the middle Ob’ river region were estimated using geoinformatic and geostatistic approaches. The largest technogenically salinized areas include oligotrophic peat soils due to the extensive spill of highly saline waters on the flat bog surface and eutrophic soils located in lower topographic positions. The natural self-purification of salinized mineral forest soils proceeds within 1–2 years after the spill. The dominant species of secondary plant communities were detected. Correlations were revealed between the residual oil and chloride contents and the total projective plant cover.     

The toxic mixing zone of neutral and acidic river water: Acute aluminium toxicity in brown trout (Salmo trutta L.)

Mixing of acid river water containing aluminium (pH 5.1, Al 345 g.l^–1) with neutral water of a lake (pH 7.0, Al 73 g.l^–1) resulted in water (pH 6.4, Al 245 g.l^–1) with a pH (6.4) and Al concentration (245 g.l^–1) expected to have low toxicity to fish on the basis of current Al toxicity models. However, under semi-field conditions the freshly mixed water (a few sec. after mixing) proved to be highly toxic to brown trout. The fish were exposed to the water at different places along a 30 m channel. At the beginning of the channel acid and neutral water were continuously mixed; the mixed water left the channel after 340 sec. The cells of the gills showed a highly increased rate of cell death by apoptosis and necrosis. Intercellular spaces were enlarged, and many leucocytes penetrated in these spaces. Mucus release was stimulated to depletion. Plasma chloride levels were hardly affected. There was a clear gradient in the deleterious effects on the fish along the channel. The fish at the beginning of the channel (about 12 sec. after mixing of the water), were severely affected, whereas the fish kept at the end of the channel (340 sec. after mixing) were only mildly affected. In the natural situation fish will relatively quickly pass through a mixing zone. In our study we therefore focused on the effects on fish after a 60 min exposure to a mixing zone (5 sec after mixing), with subsequent recovery in a region downstream of the confluence and in neutral water with low Al. The recovery in the downstream area (at the end of the channel, i.e. 5 min after mixing) was clearly hampered when compared to the recovery in neutral water with low aluminium. Thus, a short exposure to the toxic mixing zone followed by a stay in water downstream of this zone, as may occur in nature, is detrimental to migrating trout. We conclude that freshly mixed acid and neutral water contain toxic components during the first seconds to minutes after mixing, that can not be explained by current models on aluminium toxicity.     

Application of cellular and immunological biosensor techniques to assess herbicide toxicity in soils

There is growing concern about the fate and toxicity of herbicides to non‐target receptors and an increasing need to measure these analytes sensitively. The responses of cellular and immunological biosensors to four commonly used herbicides (atrazine, diuron, mecoprop and paraquat) were investigated. In combination, these sensors assess toxicity and quantify concentrations of herbicides present in extracts from soil. The bioluminescence response of the lux‐marked bacterial biosensor Escherichia coli HB101 was determined in aqueous extracts from soil to indicate toxicity. Smaller concentrations caused a toxic response for all four herbicides recovered from the Insch series than for those recovered from spiked water samples, but this was not a result of biodegradation of herbicides in the soil. This suggests that intrinsic soil factors may be altering the bioavailable fraction of herbicides, making them more toxic than equivalent concentrations in water. Herbicide concentrations were determined using immunological biosensors consisting of stabilized recombinant single chain antibodies (stAbs) specific for the four different groups of herbicides. These stAb fragments retain functionality in organic solvents such as methanol commonly used in soil extraction. Anti‐atrazine, mecoprop, diuron and paraquat stAbs were successfully used to identify and quantify herbicides present in aqueous and methanol extracts from soil. The amounts recovered from immunoassay analysis were compared with chemical analysis using high performance liquid chromatography, and the two methods correlated. These stAb fragments might provide a more rapid and sensitive means of quantifying trace amounts of herbicides and their metabolites in aqueous and methanol extracts from soil.     

An innovative stabilization/solidification treatment For contaminated soil remediation: demonstration project results

Background, aim, and scope

An innovative stabilization/solidification (S/S) process using high-performance additivated concrete technology was developed for remediating soil contaminated by metals from abandoned industrial sites. In order to verify the effectiveness of this new ex situ S/S procedure, an area highly contaminated by metallic pollutants (As, Cd, Hg, and Pb), due to the uncontrolled discharge of waste generated from artistic glass production on the island of Murano (Venice, Italy), was selected as a case study. The technique transforms the contaminated soil into an aggregate material suitable for reuse as on-site backfill. This paper reports the main results of the demonstration project performed in collaboration with the local environmental protection agency (ARPAV).

Materials and methods

An ex situ treatment for brownfield remediation, based on the transformation of contaminated soil into very dense, low porous, and mechanically resistant granular material, was set up and tested. Specific additives (water reducers and superplasticizers) to improve the stabilized material properties were developed and patented. A demonstration plant assembled on the study area to treat 6 m³ h^–1was then tested. After excavation, the contaminated soil was screened to remove coarse material. The fraction Ø?>?4 mm (coarse fraction), mainly composed of glass, brick, concrete, and stone debris, was directly reused on site after passing through a washing treatment section. The highly polluted fraction Ø?≤?4 mm (fine fraction) was treated in the S/S treatment division of the plant (European patent WO/2006/097272). The fine fraction was mixed with Portland cement and additives defined on the basis of the high performance concrete technique. the mixture was then granulated in a rolling-plate system. After 28 days curing in an onsite storage area to allow for cement hydration, the stabilized material was monitored before its in situ relocation. The chemical, mechanical, and ecotoxicological reliability and performance of the treatment was checked. Metal leachability was verified according to four leaching test methods: Italian Environmental Ministry Decree (1998), EN 12457 (2002) tout court, amended only with MgSO₄ and, lastly, with artificial sea water. The mechanical properties were measured according to BS (1990) and AASHTO (1999) to obtain the Aggregate Crushing Value and California Bearing Ratio, in that order. Moreover, leachate samples prepared with artificial seawater were assessed via the Crassostrea gigas embryotoxicity test and Vibrio fischeri bioluminescence inhibition test to discriminate the presence of potential ecotoxicological effects for the brackish and saltwater biota.

Results

Outcomes from all leachate samples highlighted the effectiveness of the remediation treatment, fully complying with the Italian legislation for non-hazardous material reuse under a physicochemical viewpoint. The stabilized granular material demonstrated high mechanical strength, low porosity, and leachability. Moreover, ecotoxicological surveys indicated the presence of low toxicity levels in leachate samples according to both toxicity tests.

Discussion

Remediated soil samples revealed a significant decrease in leachability of heavy metals as a consequence of the application of additivated cement that enhanced granular material properties, resulting in improved compactness due to the reduction in water content. The toxicity data confirmed this state-of-the-art technique, indicating that leachates could be deemed as minor acutely toxic.

Conclusions

The proposed S/S treatment proved to be able to remediate soil contaminated by heavy metals through trapping pollutants in pellet materials presenting adequate physicochemical, mechanical, and ecotoxicological properties in order to prevent leachability phenomena, their reclamation, and reuse being made easier by its granular form.

Recommendation and perspectives

This project foresees long-term monitoring activity over several years (until 2014) to consider treatment durability.