Using in situ solid phase microextraction (SPME) for depth profiling in sediments treated with activated carbon

Purpose

Sediment contamination in US waterways is an expensive and complicated issue, and as acceptance of nontraditional sediment remediation strategies broadens, novel and efficient methods to assess and monitor the bioavailability of hydrophobic organic contaminants (HOCs) in contaminated sediments will play an important role.

Materials and methods

In this project, solid phase microextraction (SPME) fibers inside perforated steel tubes were used as in situ passive samplers to measure polycyclic aromatic hydrocarbon (PAH) concentrations in sediment before and after treatment with activated carbon (AC). Two modes of waterjet amendment injection were used to apply the AC. In the first treatment, a single 2-min injection was shot into the center of a test vessel, and in the second treatment, multiple 7-s injections in a grid were placed in sediment.

Results and discussion

In the single injection, no treatment was observed 5 cm away from the injection, while at 2.5 cm, >90 % decrease of PAH pore water concentration was observed, indicating a similar bioavailability decrease. In the multiple injection experiment, >90 % PAH pore water level reductions were observed throughout the test vessel. Highly contaminated and less contaminated sediments were mixed with 0–5 % AC by weight to develop AC treatment curves. Over 99 % reduction in PAH pore water concentrations and bioavailability was observed in the less contaminated sediment at 3 % AC, while 99 % reduction was never reached even at 5 % AC addition in the highly contaminated sediment. Different treatment curves were observed for the different contaminated sediments. In situ equilibration times were 120, 215, and 250 h for phenanthrene, pyrene, and benzo(a)anthracene, respectively.

Conclusions

The results show that in situ SPME is a viable method to observe AC treatment and evaluate reductions in pore water concentrations and bioavailability.     

Sediment–pore water partition of PAH source contributions to the Yellow River using two receptor models

Purpose

Understanding the fate and behavior of polycyclic aromatic hydrocarbon (PAH) sources in aquatic systems is important for the efficiency of control policies. In this work, a new approach??organic carbon-normalized sediment?Cpore water partition coefficients of PAH source contributions (logK??_Osource)??was developed to study the sediment?Cpore water partition of PAH source contributions. The focus of this study was the Yellow River, which is the second largest river in China and one of the largest rivers in the world.

Materials and methods

Sixteen priority US Environmental Protection Agency PAHs were analyzed in 14 surface sediments and 11 pore water samples. Principal component analysis?Cmultiple linear regression (PCA-MLR) and Unmix models were employed to estimate the source contributions of PAHs in sediments and pore water samples. Finally, logK??_Osource values were calculated according to the modeled source contributions of PAHs.

Results and discussion

??PAHs (sum of the 16 PAH concentrations) in 14 sediment samples and 11 pore water samples from the Yellow River were 1,415?±?726?ng?g^?1 dry weight (dw) and 123?±?57.4???g?l^?1, respectively. The source apportionment results indicate the following: (1) for sediment samples, the contributions to ??PAHs from vehicular emissions, coal combustion, and petrogenic sources were 41.07?C61.05, 38.83?C45.56, and 11.18?C14.92?%, respectively, and (2) for pore water samples, vehicular emissions were the most significant contributor (45.51?C69.39?%), followed by petrogenic sources (29.80?C34.22?%) and coal combustion (7.35?C21.59?%). Coal combustion had the highest logK??_Osource values (4.15?C4.26) among the three categories, followed by vehicular emissions (3.51?C3.57) and petrogenic sources (3.30?C3.43).

Conclusions

The possible categories of PAH sources identified by hierarchical cluster analysis, PCA-MLR, and Unmix models were consistent, indicating that vehicular emissions, coal combustion, and petrogenic sources were three important categories. The logK??_Osource values indicate that contributions from coal combustion had a higher partition for the sediment phase compared with the other two source categories.     

Biochemical parameters in Tubifex tubifex as an integral part of complex sediment toxicity assessment

Background, aim, and scope

Restoration of lakes and reservoirs with extensive cyanobacterial water bloom often requires evaluation of the sediment quality. Next to the chemical analysis of known pollutants, sediment bioassays should be employed to assess toxicity of the present contaminants and to make predictions of associated risk. Brno reservoir in the Czech Republic is a typical example of water bodies with long-term problems concerning cyanobacterial water blooms. Comprehensive assessment of reservoir sediment quality was conducted since successful reservoir restoration might require sediment removal. An important part of this survey focused on an examination of the utility of Tubifex tubifex and its sublethal biochemical markers for the assessment of direct sediment toxicity.

Materials and methods

This complex study included chemical analysis of contaminants (heavy metals, organic pollutants), ecotoxicity testing of sediment elutriates (tests with Daphnia magna, Pseudomonas putida, Sinapis alba, Scenedesmus subspicatus), and other parameters. We have tested in more detail the applicability of T. tubifex as a test organism for direct evaluation of contact sediment toxicity. Survival tests after 14 days of exposure were complemented by an assessment of parameters serving as biomarkers for sublethal effects [such as total glutathione content (GSH), activities of the enzymes glutathione transferase (GST), glutathione peroxidase (GPx), and glutathione reductase (GR)]. The data matrix was subjected to multivariate analysis to interpret relationships between different parameters and possible differences among locations.

Results

The multivariate statistical techniques helped to clearly identify the more contaminated upstream sites and separate them from the less contaminated and reference samples. The data document closer relationships of the detected sediment contamination with results of direct sediment exposure in the T. tubifex test regarding mortality but namely regarding the sublethal endpoints rather than the results obtained with other test organisms exposed to sediment elutriates. Aside from the reduction in T. tubifex survival, the sediments with organic pollution caused an increase in glutathione content and increased activities of glutathione S-transferase and glutathione peroxidase in the exposed T. tubifex worms.

Discussion

Results of our study confirm the suitability of T. tubifex for toxicity testing of raw waters and sediments. This longer-lasting direct contact test has proven more sensitive and appropriate to reflect a lower level of pollution than do the elutriate tests. Sensitive biochemical changes in T. tubifex, including an elevation in GSH levels and GST activities, reflect a general stimulation of detoxification metabolisms in the presence of xenobiotics. The results also suggest an important role of glutathione and related enzymes in detoxification processes and possible involvement of oxidative stress in toxicity mechanisms in benthic sediment-dwelling worms such as T. tubifex.

Conclusions

The complex assessment has identified the more contaminated samples with locally increased concentration of organic pollutants and significant ecotoxicity. The direct sediment contact test with T. tubifex and especially the biochemical parameters corresponded better to the lower level of pollution than the other tests with sediment elutriates. Despite its greater time and cost demands, the direct sediment contact test can provide a more realistic picture of exposure.

Recommendations and perspectives

Sediment bioassays should always be included as an integral part of the sediment quality assessment. The direct contact tests also take into account the more hydrophobic pollutants that are not easily available for the water elution but can still be accessible to the organisms. The T. tubifex test is a suitable option for contact sediment toxicity tests also because these animals show measurable sublethal biochemical changes that can be associated with this exposure.     

Application of ionic liquids for the extraction and passive sampling of endocrine-disrupting chemicals from sediments

Purpose

The aim of this study was to assess the applicability of ionic liquids (ILs) in the extraction of organic contaminants from sediments and in passive sampling as a receiving phase material.

Materials and methods

Solutions of two water-soluble ionic liquids (WSILs)—1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIm]BF₄) and N-butyl-3-methyl pyridinium tetrafluoroborate ([BMPy]BF₄)—were used for the extraction of endocrine-disrupting chemicals (EDCs), including bisphenol A (BPA), 17β-estradiol (E2), and nonylphenol (NP), from different sediments. Furthermore, a hydrophobic IL (1-hexadecyl-3-methyl imidazolium hexafluorophosphate) was filled in a polyethylene (PE) membrane tubing to build an IL-PE passive sampler for sediment pore water. Uptake kinetics were studied by exposing samplers to sediments artificially contaminated by EDCs and identified by exposing samplers to field-contaminated sediments.

Results and discussion

EDCs were efficiently extracted by WSIL solutions from the two artificially contaminated sediments, with maximum extraction efficiencies of 84.2–104.6 % by the [BMIm]BF₄ solution and 74.9–103.7 % by the [BMPy]BF₄ solution. However, WSIL solutions are not suitable for EDC extraction from sediment with very low organic carbon contents. EDCs in sediment pore water can be efficiently taken up by the IL-PE sampler, with uptake rate constants of 2.08?×?10^?2?l?g^?1?day^?1 (BPA), 5.74?×?10^?2?l?g^?1?day^?1 (E2), and 2.10 l?g^?1?day^?1(NP).

Conclusion

BPA, E2, and NP can be extracted efficiently by IL water solution from most of the artificially and field-contaminated sediments used in this study. The IL ([HDMIm]PF₆)-PE passive sampler can be used to monitor EDCs in the pore water of sediments. A good match between the calculated and measured concentrations of BPA and E2 in pore water of field-contaminated sediments was observed.     

Chronic toxicity of fenoxycarb to the midge Chironomus riparius after exposure in sediments of different composition

Background, aim, and scope  

Fenoxycarb is an insect growth regulator widely used to control a variety of pests. As a juvenile hormone analogue, it interacts with the natural hormones involved in insect development, inhibiting metamorphosis to the adult stage. Adverse effects of fenoxycarb on non-target organisms have been repeatedly observed and its rapid dissipation from water to the organic fraction of the sediment is known. The aim of this work was to investigate the impact of fenoxycarb on the development of sediment-dwelling larvae of the midge Chironomus riparius after exposure to spiked sediment.     

The effects of suspended sediment on walleye (Sander vitreus) eggs

Purpose

Sediment resuspension is among the most widely cited concerns that lead to restricted dredging timeframes. Protection of fish species is a primary concern regarding the effects of dredging operations, yet experimental data establishing thresholds for uncontaminated suspended sediment effects are largely lacking. We conducted research to determine suspended sediment effects on walleye (Sander vitreus) egg hatching success and gross morphology following exposures mimicking sediment resuspension during dredging operations.

Materials and methods

Newly spawned eggs of northern and southern walleye strains were continuously exposed for 3?days to suspended sediment concentrations of 0, 100, 250, and 500?mg?l^?1, using sediment from Maumee Bay, OH, USA. These concentrations spanned the range measured in the vicinity of dredging operations in the Western Basin of Lake Erie.

Results and discussion

Northern and southern strain egg hatching rates were 53% and 39% of exposed eggs and 82% and 74% of viable eggs exposed, which are within reported ranges for this species. Data indicated no statistically significant effects of suspended sediment on hatching success. Gross morphological observations of exposed fry yielded no evidence of detrimental effects.

Conclusions

Experimental results indicated that walleye eggs are relatively tolerant to exposures likely to be encountered at dredging projects as performed in the Great Lakes region. Our results suggest that, given detailed knowledge of dredging project site-specific conditions and the mode of dredging to be used, better informed decisions can be made regarding adequate protective management practices. In many cases, flexibility could be given to the dredging contractor while maintaining a very low probability of risk to walleye spawning habitat.     

Toxic potential of different types of sewage sludge as fertiliser in agriculture: ecotoxicological effects on aquatic,sediment and soil indicator species

Purpose

Treated and processed sewage sludges (biosolids) generated during the treatment of wastewater usually contain substantial concentrations of nutrients, especially phosphorus, which is essential for plant growth. Sewage sludge therefore can be used as an alternative fertiliser in agriculture. But since sewage sludge could also contain pollutants, analysis and ecotoxicological tests on affected soil and stream water organisms are necessary in order to guarantee its harmless use.

Materials and methods

Three test species were chosen to cover the environmental compartments, water, sediment and soil. The following test species and parameters were applied to evaluate the acute effects of three sewage sludge samples: Lemna minor (growth inhibition, discolouration and colony breakup), Gammarus fossarum (mortality, behaviour) and Eisenia fetida (avoidance behaviour). Chemical assessment included nutrients, organic pollutants and heavy metals.

Results and discussion

The assessment of a non-dewatered sludge (S1) sample resulted in an inhibition of growth of L. minor starting from 0.6 g total solid (TS)?l^?1 after 7 days (EC₅₀ 1.2 g TS l^?1). G. fossarum displayed significantly decreased movement activity at 0.5 and 1.2 g TS l^?1 sludge concentration during an exposure time of 2 days, leading to decreased survival after 4 days of exposure in 0.5 g TS l^?1 (LC₅₀ 0.5 g TS l^?1). After 2 days, E. fetida exhibited an increased avoidance behaviour of contaminated soil from 0.2 g TS kg^?1 sewage sludge (EC₅₀ 0.4 g TS kg^?1). The dewatered sludge samples (S2 and S3) had a lower toxic effect on the test organisms. G. fossarum was the most sensitive test species in the applied test setups. The realistic application amounts of the tested sewage sludge samples of approximately 6.0 g TS kg^?1 (maximum allowed application amount of sewage sludge) and approximately 3 g TS kg^?1 (maximum agronomical relevant application amount) in worst case studies are higher than the analysed EC₅₀/LC₅₀ values of S1 and of the LC₅₀ (G. fossarum) of S2 and S3.

Conclusions

All three tested sewage sludge samples have to be classified as toxic at high concentration levels under laboratory conditions. Realistic output quantities of S1 will negatively influence soil invertebrates and freshwater organisms (plants and crustacean), whereas the dewatered sludge samples will most likely not have any acute toxic effect on the test organisms in the field. Test with environmental samples should be conducted in order to support this hypothesis.

     

Occurrence of Cu and Cr in the sedimentary humic substances and pore water from a typical sugar cane cultivation area in São Paulo,Brazil

Purpose

The purpose of this paper is to study the interactions of sedimentary humic substances (SHS) from a sugarcane cultivation area with Cu(II) and Cr(III) and to evaluate the occurrence of these metals in the pore water and SHS.

Materials and methods

For this study, the northwestern region of the State of São Paulo, Brazil, which is considered the region with the highest production of sugar cane in the state, was selected. Samples of sediment were collected from four sampling sites in the Preto, Turvo, and Grande rivers. The SHS and pore water were extracted from the sediment using the method suggested by the International Humic Substances Society and centrifugation, respectively. The complexing capacity (CC) of the SHS for Cu(II) and Cr(III) was determined by individually titrating these metals with an ultrafiltration system using tangential flow. The total concentrations of Cr and Cu were determined for the pore water, sediments, and humic substances with graphite furnace atomic absorption spectrometry and Zeeman background correction after an acid digestion, according to the methods described in US EPA Method 3050B.

Results and discussion

The SHS from a site in the Turvo River, which is typically cultivated with sugarcane, possessed the highest concentration of Cu bound to SHS (25.0%), the largest CC (0.63 mmol Cu g^?1 HS) and the highest concentration of this metal in the pore water (1.38 mg Cu Kg^?1 sed.). For Cr, the SHS collected from a location on the Preto River dam had the largest CC (0.90 mmol Cr g^?1 HS) and the lowest Cr content in the pore water (0.29 mg Cr Kg^?1 sed.), indicating that there was an inverse relationship between the CC and the concentration of metal available in the pore water.

Conclusions

Sedimentary humic substances might be one of the regulatory factors controlling the availability of Cu and Cr in the sediments found in a typical region that has been planted with sugarcane. Distinct behaviors were observed between the two elements investigated; higher CC and a larger fraction of Cu(II) were found in the pore water of samples originating from sugarcane crops. The opposite behavior was observed for the Cr(III) species.     

Characteristics of bacterial community in the water and surface sediment of the Yellow River,China, the largest turbid river in the world

Purpose

Few studies have described the bacterial community structures of turbid rivers. In this paper, the characteristics of the bacterial community in the water and surface sediment of the Yellow River, China, the largest turbid river in the world, were studied.

Materials and methods

Water and sediment samples were collected from six sites along the river. Bacterial community composition was determined using the 16S ribosomal RNA (rRNA) gene clone library technique. The relationship between environmental parameters and bacterial diversity was analyzed.

Results and discussion

A total of 1,131 gene sequences were obtained and clustered into 639 operational taxonomic units (at the 97 % identity level), with Proteobacteria as the predominant phylum. The Shannon index for water samples ranged from 3.39 to 4.40 and was generally higher than that in other rivers; this was probably due to the high suspended particulate sediment (SPS) concentration in the Yellow River, which can provide more habitats for both aerobic and anaerobic bacteria. Also, the bacterial diversity of the water samples was slightly higher than that of the surface sediment samples. The bacterial diversity of water increased along the river in the downstream direction, while there was no trend for the sediment. Redundancy analysis indicated that pH, dissolved organic carbon (DOC), and SPS were the main factors controlling the water bacterial community in the Yellow River, and pH, nitrate–nitrogen, and water content were the main factors for the surface sediment bacterial community.

Conclusions

This study indicated that the bacterial diversity of the Yellow River is generally higher than that in other rivers, suggesting that SPS plays an important role in regulating bacterial diversity and community structure in aquatic environments.     

The impact of extraction methodologies on the toxicity of sediments in the zebrafish (Danio rerio) embryo test

Purpose

Traditionally, methods for sediment extractions are characterised using chemical analyses. However, in order to evaluate sediment extracts with regard to biological effects and, thus, bioaccessibility, extraction methods have to be compared to effect data obtained from experiments with in situ exposure scenarios, i.e., sediment contact tests. This study compares four extraction methods and sediment contact test data from a previous project with respect to predictive power in the fish embryo test with zebrafish (Danio rerio).

Materials and methods

A natural and an artificial sediment spiked with a mixture of six organic pollutants (2,4-dinitrophenol, diuron, fluoranthene, nonylphenol, parathion and pentachlorophenol) were extracted using (a) membrane dialysis extraction (MDE), (b) a Soxhlet procedure, (c) hydroxypropyl-??-cyclodextrin (HPCD) or (d) Tenax^®-TA. Whereas the former two are regarded being exhaustive with respect to non-covalently bound contaminants, the latter two are considered to predict bioaccessibility. Resulting extracts were tested in the fish embryo assay with D. rerio for embryotoxic and teratogenic potential.

Results and discussion

Mortalities caused by organic extracts from Soxhlet extraction and MDE were high. However, HPCD extracts turned out to be at least as effective as extracts obtained with these two methods. One possible reason might be short ageing time of the spiked sediments. Only Tenax^®-TA extracts gave results comparable to the sediment contact assay for natural sediment, but revealed low reproducibility. Significant differences between natural and artificial sediment were found for extracts obtained with techniques using native (i.e., non-freeze-dried) sediments, i.e., HPCD and Tenax^®-TA. In contrast, MDE and Soxhlet extracts used freeze-dried sediment and did not differentiate between natural and artificial sediment. Therefore, freeze-drying has likely altered and equalised sediment properties that influence accessibility, such as composition of bacterial communities and organic matter quality.

Conclusions

Four extraction methods were successfully characterised with respect to their stringency and predictiveness for bioaccessibility. MDE was confirmed as an alternative to Soxhlet extraction. High mortalities induced by HPCD extracts underline the need to include ageing into consideration when assessing sediments. Although Tenax^®-TA may basically be used to predict bioaccessibility in the fish embryo test, the high variability observed warrants further investigation of the relation between effect and extractability. Apparently, freeze-drying can severely affect sediment properties, potentially eliminating individual properties of natural sediments.     

Investigating particle concentration effects of polycyclic aromatic hydrocarbon (PAH) sorption on sediment considering the freely dissolved concentrations of PAHs

Purpose

Suspended particulate sediment (SPS) concentration has a great impact on the sediment to water partitioning coefficients (K _p) of hydrophobic organic compounds (HOCs), which is called the particle concentration effect (PCE). However, the mechanisms regarding the PCE are not yet well understood, and there is little direct experimental evidence for these mechanisms. The aim of this study was to investigate the PCE of polycyclic aromatic hydrocarbon (PAH) sorption on sediment by analyzing the freely dissolved concentrations of PAHs.

Materials and methods

Sediments were collected from the Yellow River and the Haihe River in China. Pyrene was selected as a model PAH to investigate the sorption of PAH on sediments. In addition to the total dissolved concentration (C _TW) of pyrene, the freely dissolved concentration (C _FW) measured by polyethylene devices was used to investigate the PCE of pyrene in the presence and absence of phenanthrene and chrysene.

Results and discussion

For both the Haihe River and Yellow River sediments, in the presence and absence of other PAHs, the K _p value of pyrene with C _FW as the equilibrium concentration in the water phase was approximately two times higher than that with C _TW as the equilibrium concentration. With either C _TW or C _FW as the equilibrium concentration in the water phase, the K _p value of pyrene decreased with increasing SPS concentration as a power function. In addition, the K _p value with C _TW as the equilibrium concentration decreased faster than that with C _FW. This inferred that, apart from a third phase including dissolved organic carbon (DOC) and colloids, particle–particle, or particle–DOC interactions were important for the PCE. The contribution of the third phase to the PCE for the Haihe River sediment (72.5?±?26.4 %) was greater than the contribution for the Yellow River sediment (48.4?±?16.2 %), which had a larger particle size and lower total organic carbon and black carbon contents.

Conclusions

The PCE of PAH sorption onto sediments was attributed to both the third phase and to particle–particle or particle–DOC interactions. The contribution of the third phase to the PCE depended on both the TOC content and the particle size of sediment. As high SPS and DOC concentrations exist in many rivers, their effects on the sorption of HOCs should be considered when conducting bioavailability and ecological risk assessment.     

Nitrogen reduction in a eutrophic river canal using bioactive multilayer capping (BMC) with biozeolite and sand

Purpose

Nitrogen reduction in a eutrophic river canal using bioactive multilayer capping (BMC) with biozeolite and sand was examined through laboratory incubation experiments over 121 days.

Materials and methods

Biofilm formation on zeolite was cultivated by a mixed culture containing isolated heterotrophic nitrifiers (Bacillus sp.) and aerobic denitrifiers (Acinetobacter sp.). Two combination methods of biozeolite and sand (with two grain sizes) were used in the experiments: combination I had biozeolite on top of sand, while combination II had sand on top of biozeolite.

Results and discussion

BMC not only completely inhibited ammonium release from sediment but also reduced total nitrogen (TN) in the overlying water and sediment. On day 24, the reduction efficiencies of TN in overlying water by BMC were 60–82 %. After day 24, the long-term effectiveness of nitrogen reduction by BMC using combination II was found to be significantly better than that using combination I. Fine sand used for BMC was found to be superior to coarse sand in nitrogen reduction. Fine sand on the upper layer could strengthen biological denitrification of the biozeolite layer. The optimal BMC could reduce the amount of biozeolite and thus the costs of the technique. The TN reduction efficiency of sediment by the optimal BMC was up to 13 %.

Conclusions

BMC with biozeolite under the fine sand was found to be a feasible technique to reduce N in a eutrophic river canal.     

Conditioning of sediment polluted with heavy metals using plants as a preliminary stage of the bioremediation process: a large-scale study

Purpose

A bioremediation process for sediments contaminated with heavy metals has been developed based on two core stages: (1) conditioning of dredged sludge using plants; and (2) solid-bed bioleaching of heavy metals from the resulting soil-like material using microbially produced sulfuric acid. In laboratory and pilot-scale tests, reed canary grass (Phalaris arundinacea) was found to be best suited for the conditioning process. To demonstrate the feasibility of conditioning in practice, a study on a larger scale was performed.

Materials and methods

The sediment originated from a detritus basin of the Weisse Elster River in Leipzig (Saxony, Germany) and was polluted with heavy metals, especially with zinc and cadmium. The dredged sludge was a muddy-pasty, anoxic, and had a high organic matter content. The experimental basin (base area of 50?×?23 m) was filled with 1,400 m³ of sludge to a height of 1.2 m. Conditioning was carried out in five segments that were planted with pre-cultivated Phalaris plants at two plant densities, sowed with Phalaris seeds using two different seeding devices, and grown over by vegetation. Plant development and changing sediment characteristics were analyzed during two vegetation periods by harvesting plant biomass every 4 weeks and sampling sediment material at two different depths every 2 weeks over a total duration of 475 days.

Results and discussion

At the end of the second vegetation period, the pre-cultivated Phalaris plants had reached a height of 2 m, compared to 1.8 m for the sowed Phalaris seeds. Regarding root penetration and the degree of sediment conditioning, the less expensive sowing techniques yielded similar results to planting pre-cultivated plants. The content of heavy metals in the Phalaris plants was below the permissible limits for Germany. The vegetation evapotranspirated large amounts of water from the sediment and transported oxygen into the anoxic sludge. The water content was reduced from 68 to 37 %. The muddy-pasty sludge turned into a soil-like oxic material with a high permeability to water. The oxidation of sediment-borne compounds lowered the pH from 7.3 to 6.0. Due to the high total precipitation in Saxony in the summer of 2010, a maximum of 65 % of the sediment was conditioned.

Conclusions

The feasibility of the first core stage of the bioremediation process for sediments was demonstrated in practice by conditioning 1,400 m³ of dredged sludge using reed canary grass. To establish the proposed sediment treatment in practice, the applicability of the central core stage–solid-bed bioleaching of conditioned soil-like sediment–will also be tested at a larger scale.     

The role of stromatolites in explaining patterns of carbon, nitrogen, phosphorus, and silicon in the Se?ovlje saltern evaporation ponds (northern Adriatic Sea)

Purpose

In summer 2007, biweekly benthic fluxes of the biogenic elements carbon (C), nitrogen (N), silicon (Si), and phosphorus (P) were studied in the Se?ovlje saltern (salt-making facility) in the northern Adriatic Sea, Slovenia in order to determine the impact of stromatolite (??petola??) on the geochemical properties of saltern sediments.

Materials and methods

The brine and pore waters were analyzed for salinity, NH ₄ ⁺ , NO ₃ ^? , PO ₄ ^3? , SiO ₄ ^4? , total dissolved nitrogen, total dissolved phosphorus, and fluorescent dissolved organic matter. The sediment was analyzed for organic carbon (OC), total nitrogen (TN), total and organic phosphorus (OP), and biogenic Si concentrations, as well as values of ?? ¹³C_OC and ?? ¹⁵N_TN.

Results and discussion

Nutrient concentrations in brine water increased along the salinity gradient due to different processes, such as the evaporative concentrations of seawater, bacterial activity, more pronounced transformation and degradation of organic matter, and regeneration of nutrients. The petola from the Se?ovlje saltern, which is predominately composed of cyanobacterial and diatom communities, develops during the early evaporation stage and survives during high salinity and halite crystallization. Nitrogen fixation and P removal were the principal biogeochemical processes controlling dissolved inorganic N and P concentrations. At higher salinities, N limitation was more important. Microbes decomposed at higher salinities, and the remineralized N and P nutrients were released from surface pore waters to the brine. OP remineralization was also an important process influencing the distribution of PO ₄ ^3? concentrations in pore waters deeper in the sediments. The increasing SiO ₄ ^4? concentrations with increasing salinity in the brine waters were due to dissolution of diatom frustules, while the decrease in pore water SiO ₄ ^4? was probably the consequence of microbial uptake.

Conclusions

This study provides a better understanding of nutrient cycling and the geochemical processes in the Se?ovlje saltern.     

Ecotoxicological risk assessment of a quarry filling with seaport sediments using laboratory freshwater aquatic microcosms

Purpose

In France, contaminated seaport sediments cannot be discharged into the sea according to recent regulation. Hence, they must be managed on land. Among the solutions identified, that of filling terrestrial quarries located in the littoral zone is one of the most promising. However, this requires developing a methodology for ecological risk assessment; which was the aim of the SEDIGEST research program. In the present study, we report the results of toxicological impacts of three sediments on aquatic ecosystems close to a quarry. These results were used to formulate a risk assessment methodology.

Materials and methods

The ecotoxicological approach was based on laboratory microcosm assays applied to leachates obtained from the sediments. The microcosms contained synthetic water and sediment and five pelagic (micro-algae, duckweeds and daphnids) and benthic (chironomids and amphipods) freshwater species. The biota were exposed for 3 weeks to a range of leachate concentrations; metals were monitored in the water column and the effects (i.e. mortality, growth inhibition and midge emergence) were measured.

Results and discussion

The results showed an absence of acute toxicity at concentrations of <10% (v/v) but sublethal effects for concentrations between 1 and 10%. Given the complex nature of the leachates, it was difficult to determine the factors of toxicity. Metals, especially Cu, might have been responsible for some of the effects on the amphipods.

Conclusions

Future quarries filled with seaport sediments might emit pollutants to aquatic ecosystems in their vicinity, and risk assessors should ensure that predicted environmental concentrations of leachates are below the maximum leachate concentration acceptable for the whole ecosystem; for example, by multiplying the concentration safe for the microcosm organisms by a factor of 10.     

Evaluation of sugar beet pulp efficiency for improving the retention of copper in stormwater basin

Purpose

Sugar beet pulp (SBP) has been shown to be a promising low-cost sorbent for the removal of metals from contaminated waters. The objective of this study was to investigate the impact of SBP addition to horizontal-flow gravel filters in increasing the copper (Cu) retention ability of stormwater basins.

Material and methods

Small-scale gravel filters filled with 6 kg of a sand–sediment mix (SS) were used to experimentally treat Cu-contaminated water under conditions that represented an intense storm event. Sugar beet pulp efficiency was assessed by adding 100 g of raw SBP. Two ways of applying SBP were tested: (1) mixed with SS into the gravel filter or (2) packed at the outlet in a PVC column. Eluates were characterized by their volume, pH, Cu and dissolved organic carbon (DOC) concentrations.

Results and discussion

When placed at the outlet, SBP fixed 73 % of the Cu remaining in solution and increased the overall retention capacity of the gravel filter to 99.4 %. Conversely, when SBP was mixed with SS, the outflowing water carried higher concentrations of Cu and DOC. Complementary batch experiments underlined the crucial role of DOC in the decline of Cu sorption ability observed when SS and SBP were mixed. Geochemical calculations suggested that DOC (assumed to be pectins) promotes the mobilisation of Cu from SS by complexing it in porewater.

Conclusions

Accompanied with careful guidance, SBP has the potential of removing dissolved Cu from contaminated water in gravel filters. Protocols for SBP preparation and conditions of use should be established so as to promote its sorption efficiency and decrease its release of Cu-complexing compounds like pectins.     

Analysis of burrowing ability as a sublethal endpoint in a marine sediment bioassay with Corophium volutator (Pallas)

Purpose

Acute whole-sediment bioassay with the estuarine and marine amphipod Corophium volutator (Pallas) is widely used to assess toxicity of sediments. According to the guidelines DIN EN ISO 16712, mortality is the determined toxic endpoint. Additionally, the reburrowing ability of the surviving organisms of this acute toxicity test in fresh uncontaminated sediment is suggested as the sublethal endpoint, but insufficient information (e.g., exact measurement protocols) on this endpoint is provided, thus confounding factors and the interpretation of the results. The aim of this study was to provide information on burrowing activity as a sublethal endpoint.

Materials and methods

Amphipod tests were carried out in the laboratory, and the burrowing behavior was examined in a size- and gender-specific manner. For sediment testing, only animals of the same size were used in a defined sex ratio because it was found that female animals buried themselves faster than males and that smaller animals burrowed faster than bigger organisms. Statistical analyses were applied to determine whether burrowing time and ability differ significantly between sexes and sizes. Finally, tests were run to discern whether the burrowing ability could be a more sensitive endpoint than mortality.

Results and discussion

When the burrowing ability was examined in toxicity tests with contaminated sediment, the test organisms were affected in a dose-dependent manner. With rising concentrations of the contaminated sediment in a sublethal testing following the sediment exposure over 10 days, fewer animals buried themselves into the sediment.

Conclusions

The burrowing behavior can be used as an additional endpoint. For the tested sediment, burrowing was found to be more sensitive than the mortality. Guidance on the measurement protocol for this additional endpoint was developed. Under the test conditions examined, burrowing ability is an appropriate sublethal endpoint to supplement the toxicity test procedure.     

Historical distribution of DDT residues in pond sediments in an intensive agricultural watershed in the Yangtze-Huaihe region,China

Purpose

The extensive use of chemical pesticides on farmlands during the last several decades in China has led to a rapid deterioration of environmental water quality in recent years. The aims of this study were to: reconstruct the history of pesticide residues, determine the input load and residual load of dichlorodiphenyltrichloroethane (DDT) pesticides, and assess the risk of pesticide residues to aquatic ecosystem and human health.

Materials and methods

Caesium-137 was used to date sediment cores collected from ponds representing four land use types of an agricultural watershed with high-yield grain production and characterized by multipond systems in the Yangtze-Huaihe region of China. These ponds were selected to establish the historic pattern of DDT pesticide residues.

Results and discussion

(1) The mean total concentration of DDT residues including p,?p?′-dichlorodiphenyldichloroethylene (p,p′-DDE), p,?p?′-dichlorodiphenyldichloroethane ( p,p′-DDD), o,p′-DDT, and p,p′-DDT in sediment in the watershed was 82 μg kg^?1, ranging from under the detection limit to 457 μg kg^?1, which was mostly contributed by p,?p′-DDE (57 μg kg^?1 on average). Spatially, total concentrations of DDT residues in farmland pond sediment were the highest, reaching as high as 457 μg kg^?1. Temporally, an inflection point appeared in the 1970s, prior to which DDT contents increased with time, after which concentrations showed a decreasing trend. (2) In total, 323 kg DDT pesticide was applied to the Liuchahe Watershed since 1955. The total retention of four DDT residues in the multipond system was 14 kg (～4 % of the input), and most DDT pesticide was degraded to p,?p?′-DDE. (3) More than 80 % of sediment DDT residues exceeded their interim freshwater sediment quality guidelines, and the percentages of DDT,DDD, and DDE residues exceeding probable effect limit (PEL) values were 57, 29, and 70 %, respectively, which indicated a moderate to high ecological risk of DDT in this watershed.

Conclusions

Our results clearly reveal that the extensive use of pesticides has resulted in significant pesticide residual pollution in this watershed, which could severely deteriorate water quality and threaten aquatic ecosystem and human health in the watershed and, thus, remain a cause for concern.     

Comparison of approaches towards ecotoxicity evaluation for the application of dredged sediment on soil

Purpose

The toxicity of 36 dredged sediments from the Czech Republic was investigated using a large battery of bioassays. The aim of this study was to investigate the feasibility of ecotoxicity testing in general and of individual bioassays more specific and to investigate how the results of bioassays are determined by the physicochemical properties of sediment samples and/or sediment contamination.

Material and methods

In 2008 and 2010, 36 sediment samples were collected from rivers and ponds and from sediment heaps in different parts of the Czech Republic. Both their physicochemical properties and their levels of contamination with POPs and heavy metals were analyzed. The ecotoxicities of the sediments were evaluated using the four bioassays from the new Czech directive 257/2009 Coll. concerning the application of dredged sediments on agricultural land (Enchytraeus crypticus reproduction, Folsomia candida reproduction, Lactuca sativa root elongation, and potential ammonium oxidation). The results of the four directive bioassays were compared with the results of other soil bioassays (Caenorhabditis elegans mortality, Eisenia fetida avoidance and reproduction) and eluate bioassays (Daphnia magna immobilization, Pseudokirchneriella subcapitata growth inhibition test, and Vibrio fischeri luminescence).

Results and discussion

We demonstrate that the battery suggested in Czech directive 257/2009 Coll. is highly effective in identifying toxic samples; these bioassays clearly revealing different types of toxicity and different exposure routes. Shorter alternative bioassays may be added especially when fast toxicity identification is needed. Eluate bioassays identified samples potentially hazardous to aquatic ecosystems. Their inclusion into the assessment scheme should be considered if the goal of assessment is also the protection of aquatic ecosystems. The results of our multivariate analysis show that specific physicochemical properties and contamination may affect bioassay responses. C. elegans was the most sensitive bioassay to physicochemical properties and also to organic contamination, while eluate bioassays were sensitive to heavy metal pollution.

Conclusions

Most effects detected by the bioassays could not be explained by the levels of toxicants measured or by the natural characteristics of sediments. Our results show that bioassays are irreplaceable in dredged sediment risk assessment because they complement information provided by chemical analyses.     

DanTox—a novel joint research project using zebrafish (Danio rerio) to identify specific toxicity and molecular modes of action of sediment-bound pollutants

Introduction

The European Water Framework Directive aims to achieve a good ecological and chemical status in surface water of European rivers by the year 2015. Since sediments and particulate matter act as secondary sources for pollutants, applied sediment toxicology is perceived to play a major role for obtaining new knowledge that can contribute to successful attainment of the goal. However, the existing bioassays for sediment toxicity analyses do not provide sufficient data concerning bioavailability of environmental pollutants. In this regard, there is an urgent need to combine sediment contact assays with gene expression analysis to investigate mechanism-specific sediment toxicity.

Purpose

The aim of the novel joint research project is to develop a eukaryotic test system, which can be used to investigate the ecotoxicological effects of contaminated sediments on gene expression level (DNA-array and RT-PCR). Current ecotoxicological research customarily involves a battery of bioassays to cover different toxicological endpoints (e.g., teratogenicity, genotoxicity, mutagenicity, Ah-receptor-mediated toxicity, neurotoxicity). In contrast, methods that detect alterations in gene expression offer deeper insight by elucidating how chemical exposure and/or environmental challenge affect multiple metabolic pathways leading to these particular kinds of toxic response. Gene expression profiles reflect the way cells and organisms adapt or respond to a changing environment.

Conclusion

The present project aspires to increase the fundamental molecular and physiological knowledge concerning the mode of action of environmental toxicants in zebrafish (Danio rerio). By working with partners from the academic and research institutions as well as from industry and waterway regulations, the success of this basic research-driven joint project in terms of development and implementation of novel sediment toxicity methods will be realized.