Using sequential indicator simulation to assess the uncertainty of delineating heavy-metal contaminated soils

Mapping the spatial distribution of soil pollutants is essential for delineating contaminated areas. Currently, geostatistical interpolation, kriging, is increasingly used to estimate pollutant concentrations in soils. The kriging-based approach, indicator kriging (IK), may be used to model the uncertainty of mapping. However, a smoothing effect is usually produced when using kriging in pollutant mapping. The detailed spatial patterns of pollutants could, therefore, be lost. The local uncertainty of mapping pollutants derived by the IK technique is referred to as the conditional cumulative distribution function (ccdf) for one specific location (i.e. single-location uncertainty). The local uncertainty information obtained by IK is not sufficient as the uncertainty of mapping at several locations simultaneously (i.e. multi-location uncertainty or spatial uncertainty) is required to assess the reliability of the delineation of contaminated areas. The simulation approach, sequential indicator simulation (SIS), which has the ability to model not only single, but also multi-location uncertainties, was used, in this study, to assess the uncertainty of the delineation of heavy metal contaminated soils. To illustrate this, a data set of Cu concentrations in soil from Taiwan was used. The results show that contour maps of Cu concentrations generated by the SIS realizations exhausted all the spatial patterns of Cu concentrations without the smoothing effect found when using the kriging method. Based on the SIS realizations, the local uncertainty of Cu concentrations at a specific location of x', refers to the probability of the Cu concentration z(x') being higher than the defined threshold level of contamination (z(c)). This can be written as Prob(SIS)[z(x')>z(c)], representing the probability of contamination. The probability map of Prob(SIS)[z(x')>z(c)] can then be used for delineating contaminated areas. In addition, the multi-location uncertainty of an area A,delineated as contaminated based on the probability map of Prob(SIS)[z(x')>z(c)], can be calculated to assess the reliability of delineation. Multi-location uncertainty refers to the probability of Cu concentrations in several locations, x'(1), x'(2), em leader, x'(m,) in the area A, being higher than the threshold (z(c)) as denoted by Prob(SIS)[z(x'(1))>z(c), z(x'(2))>z(c), em leader, andz(x'(m))>z(c)] or Prob(SIS)[z(A)>z(c)]. The multi-location uncertainty Prob(SIS)[z(A)>z(c)], obtained from the SIS, can be used to assess the reliability of delineation for regions suspected of contamination, (A), which has been delineated as contaminated. Reliance on this information facilitates the decision making process in determining which areas are contaminated and require cleanup action.     

TXRF analysis of soils and sediments to assess environmental contamination

Total reflection x-ray fluorescence spectroscopy (TXRF) is proposed for the elemental chemical analysis of crustal environmental samples, such as sediments and soils. A comparative study of TXRF with respect to flame atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy was performed. Microwave acid digestion and suspension preparation methods are evaluated. A good agreement was found among the results obtained with different spectroscopic techniques and sample preparation methods for Cr, Mn, Fe, Ni, Cu, and Zn. We demonstrated that TXRF is suitable for the assessment of environmental contamination phenomena, even if the errors for Pb, As, V, and Ba are ingent.     

Influence of storage time on toxicity of freshwater sediments to benthic macroinvertebrates

Guidance concerning recommended storage times for sediments to be used in toxicity tests generally has not been based upon systematically collected experimental data. The objective of this study was to better define the effects of storage time on toxicity of a series of freshwater sediments. Sixteen sediments with varying types of contaminants were collected, homogenized and stored at 4 degrees C in 1 liter aliquots, which were periodically tested for toxicity to the amphipod Hyalella azteca and the midge Chironomus tentans after storage times of up to 101 weeks. The sediments ranged from non-toxic to extremely toxic (100% mortality) in 10-day assays, with several of the samples displaying an intermediate degree of toxicity (e.g. partial mortality, reduced growth). Biological responses in most of the samples did not vary with time relative to their statistical relationship to control values; samples identified initially as toxic (or non-toxic) tended to remain toxic (or non-toxic) regardless of when they were tested. The variations that were observed in biological responses over time generally were not systematic; that is, there were no apparent trends in samples becoming more (or less) toxic in the 10-day assays. This suggests that the source of at least some of the temporal changes in toxicity were due to inherent biological variability of the assays used to assess the sediments, rather than the effects of storage. In C. tentans tests with the least toxic sediments, among-replicate variability tended to be greater in initial assays than in tests with samples that had been stored for some period of time. This may have been due to the presence of indigenous competitive or predatory organisms that did not survive during prolonged storage.     

A multibiomarker approach using the polychaete Arenicola marina to assess oil-contaminated sediments

Background, aim and scope  

Marine and coastal sediments can accumulate substantial concentrations of metals and hydrocarbons, yet the consequences of this contamination for exposed biota in situ can be difficult to establish. Here, we examine the hypothesis that exposure to contaminated sediments can lead to detrimental effects in sediment-dwelling species. The combination of chemical and biological assessment allows the identification of the impact of chemical contamination, and their use as assessment tools is becoming increasingly important.     

Comparison of solid and liquid-phase bioassays using ecoscores to assess contaminated soils

Bioassays on aqueous and solid phases of contaminated soils were compared, belonging to a wide array of trophic and response levels and using ecoscores for evaluating ecotoxicological and genotoxicological endpoints. The method was applied to four coke factory soils contaminated mainly with PAHs, but also to a lesser extent by heavy metals and cyanides. Aquatic bioassays do not differ from terrestrial bioassays when scaling soils according to toxicity but they are complementary from the viewpoint of ecological relevance. Both aquatic and terrestrial endpoints are strongly correlated with concentrations of 3-ring PAHs. This evaluation procedure allows us to propose a cost-effective battery which embraces a wide array of test organisms and response levels: it includes two rapid bioassays (Microtox(?) and springtail avoidance), a micronucleus test and three bioassays of a longer duration (algal growth, lettuce germination and springtail reproduction). This battery can be recommended for a cost-effective assessment of polluted/remediated soils.     

Differential responses of benthic microbes and meiofauna to fish-farm disturbance in coastal sediments

Bacterial and meiofaunal abundance and biomass and their response to the disturbance induced by fish-farm biodeposition were investigated from March to October 1997 on a monthly basis at two stations of the Gaeta Gulf (Tyrrhenian Sea, Mediterranean Sea). The biopolymeric fraction of the organic matter was characterized by high concentrations which was similar at both fish-farming-impacted and control stations. Similarly, bacteria accounted for a small fraction of the biopolymeric organic carbon (< 1%), while the contribution due to auto-fluorescent cell biomass (i.e. prokaryotic and eukaryotic cells displaying auto-fluorescence) to the total biopolymeric carbon was quantitatively negligible (< 0.1%). Benthic bacteria appear to be sensitive to organic enrichment as their abundance increased significantly beneath the cage, whilst numbers of meiofauna was lower than in the control. Changes occurred also in terms of individual nematode biomass that increased as result of the biodeposition. A particularly useful tool appeared to be represented by the ratio of benthic auto-fluorescent cells to bacterial abundance, bacteria to meiofaunal biomass and auto-fluorescent cells to meiofauna biomass. All these parameters described well the impact due to biodeposition on the benthic environment as their ratios displayed significantly higher values in farm sediments, but recovered rapidly (15 days) to values observed in the control (i.e. undisturbed conditions) immediately after cage removal. Changes observed in the present study highlight that the increased organic loading determined a shift of the relative contribution of the different benthic components to the total biopolymeric carbon, so that in highly impacted systems total benthic biomass becomes increasingly dominated by microbial components.     

A simplified approach to modelling underground migration of radionuclides from contaminated river sediments

Accidental releases of waste water from the first Czechoslovak nuclear power plant, A1, caused contamination of sediments of the Dudváh river, flowing into the Vah river, in Slovakia. Rather high concentrations of ¹³⁷Cs and ⁹⁰Sr (2150Bq dm⁻³ and 215Bq dm⁻³, respectively) were found in bottom sediments of a former channel of the re-engineered river body at a distance of about 250 m from a village, Siladice, with water-supply wells. In order to assess the possibility of contamination of the wells, underground migration of both radionuclides from the contaminated area was simulated using an original layered convection-diffusion model. K_d values determined in laboratory experiments were used. The analysis of the hydrological situation in the area reveals that the critical condition is a dominant horizontal groundwater flow near the water table in the direction from the Váh bank to Siladice, in the periods when the contaminated body lies under the water table. The simulation calculated under conservative conditions showed that the contamination of water-supply wells would not exceed permissible concentration limits.     

Using multiple indices to evaluate scenarios for the remediation of contaminated land: the Porto Marghera (Venice,Italy) contaminated site

Background, aim, and scope  

The management of contaminated sites requires the investigation of different involved aspects (from socioeconomic to risk and technological issues) and the presentation of useful and condensed information to decision makers. For this purpose, indices are more and more recognized as effective and valuable tools. This paper presents specific indices created within the DEcision Support sYstem for REhabilitation of contaminated sites (DESYRE).     

Change of magnetic properties due to fluctuations of hydrocarbon contaminated groundwater in unconsolidated sediments

Sediments affected by fluctuations of hydrocarbon contaminated groundwater were studied at a former military site. Due to remediation, groundwater table fluctuation (GWTF) extends over approximately one meter. Three cores were collected, penetrating through the GWTF zone. Magnetic parameters, sediment properties and hydrocarbon content were measured. We discovered that magnetic concentration parameters increased towards the top of the GWTF zone. Magnetite is responsible for this enhancement; rock magnetic parameters indicate that the newly formed magnetite is in a single domain rather than a superparamagnetic state. The presence of hydrocarbons is apparently essential for magnetite to form, as there is clearly less magnetic enhancement in the core, which is outside of the strongly contaminated area. From our results we conclude that the top of the fluctuation zone has the most intensive geomicrobiological activity probably responsible for magnetite formation. This finding could be relevant for developing methods for simply and quickly detecting oil spills.     

Using expectations of gain to bound the benefits from contaminated land remediation

Current risk-based decision-making techniques for prioritising contaminated land for clean-up have been criticized within Hungary for their failure to consider remediation benefits. A cost-benefit or risk-benefit approach is required to ensure that scarce resources for remediation are used efficiently. Problems arise because the credibility of non-market valuation information in Hungary is low, yet estimates of the value of non-market goods are required if cost-benefit approaches to decision-making are to be used effectively. This paper suggests using multiple techniques to bound 'true' values of non-market goods in order to enhance the potential use of environmental valuation information. A dichotomous-choice contingent valuation survey and a property-owner valuation survey were carried out in the vicinity of a hazardous waste site on the edge of Debrecen, Hungary. The aim of the study was to explore the potential for using these techniques to measure the benefits from contaminated site remediation in Hungary. The two surveys provide lower and upper bounds on expected benefits from clean-up aggregated results indicate that remediation benefits range from US$2.59 million to US$12.4 million.     

Integration of toxicological and chemical tools to assess the bioavailability of metals and energetic compounds in contaminated soils

Bioavailability is critical for understanding effects that might result from exposure of biota to contaminated soils. Soils from military range and training areas (RTAs) are contaminated principally by energetic materials (EM) and metals. Their chemical characteristics are relatively well known and toxicity assessment of soils from RTAs are in some cases available. However, bioavailability on these sites needs to be comprehensively characterized. A holistic approach to bioavailability, incorporating both chemical and earthworm toxicological indicators, was applied to soils from an anti-tank firing range at a Canadian Forces Base. Results showed that HMX and the metals Zn, Pb, Bi and Cd, though not consistently the prevailing toxicants, were the most accessible to earthworms. Some metals (notably Cu, Zn, Cr and Bi) were also accumulated in earthworm tissue but those were not necessarily expected given their bioaccessibility (i.e., the chemical availability of contaminants in the environment for the organisms) at the beginning of the exposure. The tested soils impaired earthworm reproduction and reduced adult growth. Measurement of selected sublethal parameters indicated that lysosomal integrity (determined as the neutral red retention time--NRRT) was decreased, while elevated superoxide dismutase (SOD) activity suggested that earthworms experienced oxidative stress. The correspondence between the NRRT and metal contamination pattern suggested that metals may be the main cause of lysosomal disruption in EM-contaminated soils. The approach to bioavailability appraisal adopted in this case appears to be a promising practice for site-specific assessment of contaminated land.     

Oxidation of acid-volatile sulfide in surface sediments increases the release and toxicity of copper to the benthic amphipod Melita plumulosa

Acid-volatile sulfides (AVS) are an important metal-binding phase in sediments. For sediments that contain an excess of AVS over simultaneously extracted metal (SEM) concentrations, acute or chronic effects should not result from the metals Cd, Cu, Ni, Pb and Zn. While AVS phases may exist in surface sediments, the exposure to dissolved oxygen may oxidize the AVS and release metals to more bioavailable forms. We investigated the role of oxidation of AVS, and specifically copper sulfide phases, in surface sediments, in the toxicity to juveniles of the epibenthic amphipod, Melita plumulosa. Sediments containing known amounts of copper sulfide were prepared either in situ by reacting dissolved copper with AVS that had formed in field sediments or created in sediments within the laboratory, or by addition of synthesised CuS to sediments. Regardless of the form of the copper sulfide, considerable oxidation of AVS occurred during the 10-d tests. Sediments that had a molar excess of AVS compared to SEM at the start of the tests, did not always have an excess at the end of the tests. Consistent with the AVS-SEM model, no toxicity was observed for sediments with an excess of AVS throughout the tests. However, the study highlights the need to carefully consider the changes in AVS concentrations during tests, and that measurements of AVS and SEM concentrations should carefully target the materials to which the organisms are being exposed throughout tests, which in the case of juvenile M. plumulosa is the top few mm of the sediments.     

Selective supercritical fluid extraction to estimate the fraction of PCB that is bioavailable to a benthic organism in a naturally contaminated sediment

Selective supercritical fluid extraction (SFE) at 40 degrees C, 120 bar and 60 min was utilised as a means to estimate the bioavailable fraction of PCBs to chironomid larvae in a naturally contaminated limnic sediment. This extraction methodology removed about 50% of the PCBs from the sediment. According to the equilibrium partitioning theory, organisms in that sediment should decrease their uptake from the sediment to the same extent, biota-to-sediment accumulation factors (BSAFs) thus remaining constant. Surprisingly, the BSAFs for 11 PCB congeners decreased some 40% for the selectively extracted sediment as compared to BSAFs for organisms dwelling in untreated sediment. The results were statistically significant at the 0.001 level using a paired t-test. This can only be interpreted so that selective SFE removed easily available PCBs preferentially, leaving more tightly bound PCBs behind. Hence, by fine-tuning extraction conditions, this methodology might be used to estimate bioavailable fractions by chemical means.     

Effect of modified Fenton treatment on the thermal behavior of contaminated harbor sediments

This study presents the results of experimental Fenton-like treatments conducted on marine sediment slurries (2g sediment vs. 20 ml liquid). The sediment was collected in a harbor situated in a high density industrial area, characterized by a great hydrocarbon C>12 and PAHs contamination. The investigated parameters were: the H(2)O(2) dose, the reagent's pH and the effect of a phosphate salt and ferrous iron addition. To evaluate sediment's characteristics COD, particle size, thermogravimetric and differential thermal analyses were performed under N(2) and O(2) atmosphere while dissolved organic carbon and COD analyses were performed on the filtrate. Results indicate that the treatment was able to change the organic matter to a less hydrophobic state, to destroy part of the organic carbon (up to 78% decrease of the 200-400 degrees C labile organic matter), to lower the COD of the sediment (60% COD removal maximum) and to increase the cumulated distribution undersize. In addition as the treated sediment showed easier-to-handle characteristics, reduced caking and lower aggregation capacity, the modified Fenton treatment could also be considered a pre-treatment of a successive thermal treatment.     

Evaluation of time-to-effects as a basis for quantifying the toxicity of contaminated sediments

Due to uncertainties as to appropriate procedures and dilution materials, most sediment tests are conducted only with undiluted, whole samples. Hence, it is not possible to use conventional concentration-response approaches to quantify toxicity of samples that elicit a 100% effect (e.g., mortality) at a preset test interval (typically 10 d). An alternative approach to quantifying the relative toxicity of test sediments is to determine time-to-effects. The objective of this study was to assess the utility of a time-to-effects approach for quantifying toxicity of freshwater sediments to the invertebrates Hyalella azteca and Chironomus tentans. Survival of both species and growth of C. tentans was determined using five sediments (four test samples and a control sediment) by destructively sampling replicate test chambers over the course of a "standard" 10-d assay. Studies with the control sediment and a non-toxic test sample indicated excellent recovery of test animals, even early in the test (e.g., <24 h) when individuals of both species are relatively small. Reasonable, typically monotonic, time-to-death relationships were observed for both H. azteca and C. tentans exposed to three comparatively toxic test sediments, all of which caused significant mortality by 10 d. Use of the time-to-effects approach allowed expression of toxicity of the three samples relative to one another, as well as documentation of decreases in toxicity of one of the sediments with increased storage time. These studies demonstrate the feasibility of use of time-to-effects as a basis for quantifying the relative toxicity of contaminated sediments.     

Use of the physiologically-based extraction test to assess the oral bioaccessibility of metals in vegetable plants grown in contaminated soil

The oral bioaccessibility of metals in vegetable plants grown on contaminated soil was assessed. This was done using the physiologically-based extraction test (PBET) to simulate the human digestion of plant material. A range of vegetable plants, i.e. carrot, lettuce, radish and spinach, were grown on metal contaminated soil. After reaching maturity the plants were harvested and analysed for their total metal content (i.e. Cr, Cd, Cu, Fe, Mn, Mo, Ni, Pb and Zn) by inductively coupled plasma-mass spectrometry (ICP-MS). The plant samples were then subsequently extracted using an in vitro gastrointestinal approach or PBET to assess the likelihood of oral bioaccessibility if the material was consumed by humans.