Monitoring of subaqueous depots with active barrier systems for contaminated dredged material using dialysis samplers and DGT probes

Background, Aims and Scope  Disposal of dredged material in subaqueous depots is increasingly considered an economic and ecologically sound option in managing contaminated dredged material. The concept of subaqueous disposals capped with active barrier systems has been developed to minimize this risk of contaminant release. As such a depot represents a permanent installation within a sensitive ecosystem, it requires a thorough monitoring concept. It is the goal of this work to develop such a concept regarding general considerations and results of laboratory and field investigations. Methods  In addition to the state-of-the-art techniques developed for other under-water constructions, this monitoring concept is developed with particular respect to the chemical isolation of the dredged material from the overlying water body. It comprises the use of seepage meters, dialysis samplers, and DGT gel probes for determining the migration of selected target solutes. The capability of the dialysis samplers is demonstrated by comparing field results with model calculations. The appropriateness of DGT probes to assess the impact of humic substances on trace metal speciation and on copper toxicity is demonstrated with the aid of laboratory experiments. Results and Discussion  The experimental results show that, by using dialysis samplers, the temporal changes in concentration-depth-profiles of heavy metals in the pore solution can be monitored. Additionally, the application of DGT probes facilitates the in situ detection of labile species of a metal in the presence of dissolved humic substances, which serves to reflect its toxicity. Conclusions. Three subsequent monitoring phases are distinguished on the basis of both general considerations and the findings from field results: A hydraulic phase that is characterized by compaction and pore water expulsion, a geochemical phase in which the demobilization of pollutants can occur due to substantial changes in the physico-chemical conditions (pH, EH), and a steady-state-phase where pore water flow and geochemical conditions are approaching their minimum. Recommendations and Outlook  The monitoring concept suggested here provides a versatile tool to assess the chemical isolation of subaqueous sediment depots and other contaminated sediment sites. This is of great importance as subaqueous disposal is increasingly considered a future management strategy as space for upland disposal is limited and treatment, in general, proves to be too costly.     

Importance of dose metrics for lethal and sublethal sediment metal toxicity in the oligochaete worm Lumbriculus variegatus

Background, Aims, and Scope  There is an increasing demand for controlled toxicity tests to predict biological effects related to sediment metal contamination. In this context, questions of metal-specific factors, sensitivity of toxicity endpoints, and variability in exposure duration arise. In addition, the choice of the dose metrics for responses is equally important and is related to the applicability of the concept of critical body residue (CBR) in exposure assessments, as well as being the main focus of this study. Methods  Experiments were conducted to assess toxicity of Cd, Cr, Cu and Pb to the oligochaete worm Lumbriculus variegatus with the aim of determining CBRs for two response metrics. Mortality and feeding activity of worms exposed to sediment-spiked metals were used as end-points in connection with residue analyses from both the organisms and the surrounding media. Results  LC50 values were 0.3, 1.4, 5.2, and 6.7 mg/L (from 4.7 μmol/L to 128.0 μmol/L), and the order of toxicity, from most toxic to least toxic, was Cu > Cd > Pb>Cr. By relating toxicity to body residue, variability in toxicity among the metals decreased and the order of toxicity was altered. The highest lethal residue value was obtained for Cu (10.8 mmol/kg) and the lowest was obtained for Cd (2.3 mmol/kg). In the 10-d sublethal test, both time and metal exposure were an important source of variation in the feeding activity of worms. The significant treatment effects were observed from worms exposed to Cd or Pb, with the controls yielding the highest feeding rate. However, quantitative changes in the measured endpoint did not correlate with the exposure concentrations or body residues, which remained an order of magnitude lower than in the acute exposures. Discussion  Both response metrics were able to detect a toxic effect of the metals. However, the ranking of metal toxicity was dependant on the choice of the dose metric used. An attempt to form a causal mortality-mediated link between tissue residues and metal toxicity was successful in water-only exposures. The results also indicated that egestion rate was a sensitive toxicity end point for predicting the effects of sediment contamination. Conclusions  By relating the biological response with the tissue metal residues, toxicity data was comparable to both environmental media as well as different response metrics and time scales. The results also revealed the importance of metal toxicity ranking on a molar basis and, furthermore, a direct link to the CBR concept was established. Recommendations and Perspectives  There is a growing demand for methods to assess the effects of contaminated sediments to benthic fauna and whole aquatic ecosystems. Such information is needed for sediment quality guidelines that are currently being developed in many countries and remediation processes. The use of body residues as a dose metric in metal toxicity studies may help to overcome difficulties related to bioavailability issues commonly faced in sediment toxicity studies. ESS-Submission Editor: Prof. Dr. Henner Hollert (henner.hollert@bio5.rwth-aachen.de)     

A new plant-based bioassay for aquatic sediments

Background, Goal and Scope  To date, standardised bioassays for the assessment of the ecotoxicological potential in sediments and dredged material use test organisms like bacteria, algae and crustaceae. This paper presents the development and application of a novel sediment contact test (whole sediment) withMyriophyllum aquaticum, a representative of rooted aquatic macrophytes. The aim of the present study is to demonstrate the value of a sediment contact test with rooted macrophytes as a supplement to existing test batteries in order to improve the assessment of sediment toxicity. Methods  The newly developed sediment contact test withMyriophylhim aquaticum was applied to natural whole sediments. For performing the test, whorls ofMyriophyllum aquaticum were directly planted in the native sediment and incubated in the light at 24°C (cf. section results and discussion). The end points of the test were the number of the shoots and the fresh weight of the whole plants. The duckweed growth inhibition test withLemna minor according to ISO/DIS 20079 was performed in pore waters from sediment samples. The results of the sediment contact test withMyriophyllum aquaticum were compared with each other and with those of the aquatic duckweed test. Results and Discussion  A test protocol for the new plant-based sediment contact test using the aquatic plantMyriophyllum aquaticum as an indicator was developed. The best control sediment proved to be the OECD sediment (OECD 207). A test period of 10 days appeared to be sufficient for the test. The increase of biomass and the derived growth rate were found to be the most suitable evaluation parameters. The growth behaviour ofMyriophyllum aquaticum differed depending on the origin of sediments. Therefore, plant-affecting contamination, that is bound in sediments, was indicated. Conclusions  The novel sediment contact test withMyriophyllum aquaticum can indicate phytotoxic effects in sediments. Therefore, it allows a better assessment of the overall-toxicity in whole sediments. Recommendations and Outlook  The sediment contact test withMyriophyllum aquaticum is a valuable tool for the evaluation of the ecotoxicological risk potential of waters and sediments. It should become a complement to a standardised test battery generally used for the assessment of sediment toxicity.     

Contaminated sediments as a potential source of Zn, Pb, and Cd for a river system in the historical metalliferous ore mining and smelting industry area of South Poland

Background, aim, and scope  Elevated levels of heavy metals in the aquatic and soil systems can be caused by the weathering of mineralized rocks. This enrichment is often considerably enlarged by historical and current mining and smelting activities. In Poland, the most contaminated river systems are those in the Silesia region. The metalliferous ore mining and smelting industries have been the main sources of heavy metal pollutions over the last 100–170 years. The previous and present studies have shown very high concentrations of heavy metals in the bottom sediments of the Mala Panew River, the most polluted tributary of the Oder River. The main objective of this work was to study temporary changes of selected metal (Zn, Pb, and Cd) concentrations in upper layer of bottom sediments at the measuring point near the outlet of the Mala Panew River into the Oder River, and to determine the vertical distribution of the metals in the sediment cores from the most polluted middle part of this river. The mobility of the metals and their potential bioavailability were assessed based on metal partitioning in the sediments and metal concentrations in pore waters. The presented data were compared with metal concentrations in aquatic sediments from similar historical mining and smelting sites in Poland and other countries. Methods  The upper layer of bottom sediment samples from the same Mala Panew River measuring point were collected six times in the period 1997–2005, while five sediment cores were collected once from the middle course of Mala Panew River in 2006. Abiotic parameters such as pH and Eh have been determined in situ. Metal contents were determined in the <20 and <63 μm size fractions of sediments after digestion in a microwave oven with aqua regia or concentrated nitric acid. Metal mobility was assessed in the selected sediment cores by the chemical forms of metals (sequential extraction method) and their concentrations in pore waters were investigated. Results  The concentrations of Cd, Pb, and Zn in the upper layer of sediments varied, depending on both the season and the year of sampling. Their mean concentrations (from six samplings) are [mg/kg]: Zn 1,846, Pb 229 and Cd 73. The metal concentrations in the sediment cores varied with the depth in the range of [mg/kg]: 0.18–559 for Cd, 26.2–3,309 for Pb and 126–11,153 for Zn, although the highest accumulations generally could be observed in the deeper layers. The most mobile metal fractions, i.e., exchangeable, carbonate and easily reducible fractions, are typical of Zn and Cd. Cadmium was found to be the most mobile metal and its relative contribution ranges from 84 to 96%, while in the case of Zn it ranged from 45 to 94%. Lead is mainly associated with the moderately reducible fraction (30–60%). Relative contributions of metal chemical forms slightly vary with the depth in the sediment profile. The results obtained for the pore water samples show very high concentrations of the metals studied, especially in the case of Cd (31–960 μg/dm³) and Zn (300–4,400 μg/dm³). Discussion  Accumulation of Cd, Pb, and Zn in the upper layer of the bottom sediments and in the sediment core samples from the Mala Panew River is very high, considerably exceeding the local geochemical background. High contributions of mobile Cd and Zn and the toxicity of cadmium can cause environmental risk. Our measurements also suggest that mobile metals can migrate into groundwater, whereas the groundwater itself can leach some chemicals from river sediments, because of a relatively high water table in the study area, especially during rainfall periods. Comparison of the results obtained with the literature data from the last decade shows that the concentrations of Cd and Zn in the sediments from the Mala Panew River are the highest among other submersed sediments in Poland and other regions (e.g., the Mulde River, Germany). Conclusions  The Mala Panew River is one of the most polluted rivers when compared with similar historical mining and smelting areas in Poland and elsewhere. The sediments studied are strongly polluted with the metals analyzed. In the upper layer of the bottom sediments there has been no reduction of Zn and Cd amounts over the last decade, which could suggests a long-term migration and a secondary contamination. Considerably higher accumulations of metals in overbank sediment cores and in the deeper core section could result from strong contamination in previous decades and translocation of Cd and Zn (secondary pollutants). The relatively high concentrations of the two metals in pore waters support these findings. Cadmium is crucial in the environmental risk assessment because of its high mobility and toxicity. These data are important for water/sediment management in the transboundary Oder River catchment, situated in Poland, Germany and the Czech Republic. Recommendations and perspectives  It is important to assess mobility phase and pore water in the contaminated historical aquatic sediments. Such studies may help explain the changes, which take place in the sediment layers as well as at the water–sediment interface. Obtained results should be used for the risk assessment of the historical contaminated sediments at the local river-basin scale. The treatment of contaminated sediments, e.g., dragging activity, should be considered as very important in management strategies in order to avoid remobilization of metals.     

The ability of the DGT soil phosphorus test to predict pasture response in Australian pasture soils – a preliminary assessment

Diffusive gradients in thin‐films (DGT) technology provides an alternative assessment of available phosphorus (P) for a range of crops, suggesting a preliminary examination of the performance of the new DGT‐P test, compared to existing bicarbonate extractable Olsen and Colwell P tests, for pastures is justified. This study utilized historic data from the Australian National Reactive Phosphate Rock (NRPR) study (1992–1994) that included 25 experimental sites representing a wide range of soil types and climates used for pasture production. Stored (~19 yr) soil samples were analysed for DGT‐P, Olsen P and a single point P buffering index (PBI) and re‐analysed for Colwell P. Results showed the traditional bicarbonate extractable Colwell (r² = 0.45, P < 0.001) and Olsen P (r² = 0.27, P < 0.001) methods predicted relative pasture P response more accurately, compared to the novel DGT‐P test (r² = 0.09, P = 0.03) when all 3 yr of data were examined. We hypothesize that the harsher bicarbonate extraction used for the Olsen and Colwell methods more accurately reflects the ability of perennial pasture roots to access less labile forms of P, in contrast to the DGT‐P test, which does not change the soil pH or dilute the soil and appears unable to fully account for a plants ability to solubilize P. Further studies are needed to compare the capacity of DGT‐P to measure P availability in perennial pasture systems and to better understand the soil chemical differences between pasture and cropping systems.     

Determination of High Resolution Pore Water Profiles of Trace Metals in Sediments of the Rupel River (Belgium) using Det (Diffusive Equilibrium in Thin Films) and DGT (Diffusive Gradients in Thin Films) Techniques

The techniques of diffusional equilibrium in thin films (DET) and diffusional gradients in thin films (DGT) were used to obtain high resolution pore water profiles of total dissolved and labile trace (mobilizable) metals in the sediments of the Rupel River, Belgium. DGT measures labile metal species in situ by immobilizing them on a resin gel after diffusion through a diffusive gel whereas for DET an equilibrium is established between the DET gel and the pore water. Concentrations of Pb and Zn obtained by DGT were in good agreement with the results obtained by centrifugation, and thus were well buffered by rapid equilibrium with the solid phase, whereas Fe, Mn and Cd were very tightly bound to the sediment phase and large differences were observed between the labile and the total metal concentrations. Cu, Zn, Co and Ni show intermediated behavior. Good correlations were found between the profiles of As and Fe and Mn and Co for DET as well as DGT showing a close link between the geochemical behavior of these elements. Cu, Zn, Pb and Cd are also influenced by the reductive mobilization of Fe and Mn oxides but are also closely linked to the bacterial degradation of organic matter in the surface sediments as to the precipitation of metal sulfides in the deeper layers.     

Application of a new sediment contact test with <Emphasis Type="Italic">Myriophyllum aquaticum</Emphasis> and of the aquatic <Emphasis Type="Italic">Lemna</Emphasis> test to assess the sediment quality of Lake Skadar

Goal, Scope and Background  Situated in the transboundary belt between Montenegro and Albania, Lake Skadar is the largest freshwater reservoir in Southeastern Europe. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Skadar and its extensive adjacent wetlands are internationally recognised as a site of significance and importance (Ramsar site). Within the last 10 to 20 years, Lake Skadar was exposed to intensive pollution. For the assessment of the ecotoxic load of the sediments sampled in Lake Skadar, a triad approach was recently applied. Overall, a complex spectrum of ecotoxic loads was elucidated. The aim of the present study was to use plant-based bioassays for assessing the sediment quality of Lake Skadar in order to facilitate and complement the triad test battery. The newly developed sediment contact test with Myriophyllum aquaticum and the aquatic growth inhibition test with Lemna minor were applied to native sediments and pore water, respectively, allowing the investigation of different toxicity-effects caused by particle-bound pollutants as well as pollutants in the interstitial water. This investigation is the first application of the novel sediment contact test with Myriophyllum aquaticum to lake sediments. Methods  Sediment samples were taken from nine selected sites at Lake Skadar and investigated by the sediment contact assay with Myriophyllum aquaticum. The pore water was extracted from these sediment samples to be analysed in the aquatic growth inhibition test with Lemna minor. The results of the sediment contact tests were compared with each other and with those of the aquatic growth inhibition test. Results and Discussion  Both applied macrophyte biotests revealed distinct changes in the growth behaviour of the two macrophytes subsequent to the exposure to the investigated natural sediments of Lake Skadar. The Myriophyllum sediment contact test revealed significant toxicity in the sediment samples from Radus and Kamenik, whereas the aquatic Lemna test showed inhibition effects for the samples from Sterbeq, Plavnica and Kamice. Data obtained with the newly developed Danio rerio contact test and the Arthrobacter globiformis contact test confirmed the Myriophyllum results. Analyses of the heavy metal content in the sediments revealed low or moderate contamination levels. Correlation analyses between the content of heavy metals in the sediments and growth inhibition of Myriophyllum aquaticum showed a significant correlation between Cr concentrations and growth inhibition. Comparable findings are available for a German river system. In contrast, no significant correlation between inhibition rates and concentration of metals could be observed with Lemna minor. Conclusions  It was shown that the newly developed sediment contact test with Myriophyllum aquaticum is applicable to lake sediments. In both the sediment contact test with Myriophyllum aquaticum on whole sediments and the aquatic growth inhibition test with Lemna minor on pore water, plant growth was influenced by the natural sediments and its components. Therefore, both test systems were found to be suitable for the detection of phytotoxic effects upon exposure to sediments. Myriophyllum aquaticum as test organism of the contact test grows directly in the sediment without an additional water-layer. Thus, it is able to detect toxicity caused by particle-bound phytotoxic substances as well as pore water-related contamination, while the floating Lemna minor can only detect effects emanating from pore water. Significant differences of the results were observed between these two test systems and, accordingly, the two different exposure scenarios. Hence, none of the tests can replace the other one and, as a consequence, both should be included into a test battery for the assessment of sediment toxicity. Recommendations and Perspectives  Both plant assays were shown to be reliable tools for the evaluation of the eco-toxicological risk potentials of pore water and solid-phase sediment. They should become a complement to the standardised test battery generally used for comprehensive hazard assessment. ESS-Submission Editor: Dr. Ulrike Kammann (ulrike.kammann@ifo.bfa-fisch.de)     

Long-term observations of the vertical distributions of mineral elements and phosphorus dynamics in sediments in a shallow eutrophic lake in Japan

Purpose

To explore the mechanisms in the deposition and release of phosphorus (P) in the sediment of a shallow eutrophic lake using preserved samples, we investigated the vertical and temporal changes in P, manganese (Mn), sulfur (S), iron (Fe), aluminum (Al), calcium (Ca), and magnesium (Mg) in the sediment samples and the phosphate in the sediment pore water samples over a period of 6 years.

Materials and methods

The upper 15 cm of sediment from Lake Kasumigaura in Japan was collected monthly from 2003 to 2008 from the center of the lake. Sediment cores were divided into seven depth segments and were acid-digested for an elemental analysis via inductively coupled plasma atomic emission spectroscopy. Phosphate concentrations of the sediment pore water were determined using the molybdenum blue method. A multiple regression analysis was conducted by setting the P content as the response variable and Mn, S, Fe, Al, Ca, and Mg as explanatory variables.

Results and discussion

The results of the multiple regression analysis demonstrated that P co-precipitates with Fe and Al oxides and accumulates on the sediment surface. The vertical distributions of Mn and S suggest that Mn reduction occurs within the 0–1-cm-depth layer of the sediment and that iron sulfide is actively formed in the 6–10-cm-depth layer of the sediment. These findings imply that the layer in which ferric oxides are reduced to ferrous ions is present near the 1–6-cm-depth layer of the sediment. This layer corresponds to the layer in which the maximum phosphate concentration of the sediment pore water often occurred (the 2–6-cm-depth layer). These results indicate that vertical distributions of mineral elements are useful for assessing P dynamics in sediments.

Conclusions

The lake sediments record the dynamics of P in the sediment. Our analytical approach using long-term observation data demonstrated that the accumulation and release of P associated with a change in the redox state can be assessed based on the vertical distributions of mineral elements in the lake sediments.

     

Geochemical Mobility and Bioavailability of Heavy Metals in a Lake Affected by Acid Mine Drainage: Lake Hope, Vinton County, Ohio

Sandy Run (Vinton County, southeastern Ohio, USA) is a stream receiving acid mine drainage (AMD) from an abandoned coal mine complex. This stream has been dammed to form Lake Hope. The heavy metal composition of waters (benthic and pore), sediments, and macroinvertebrates in the lake reservoir sediments were analyzed. Lake waters contained Mn as the heavy metal present in higher concentrations followed by Fe, Al, and Zn. Depletion of Fe and Al occurred from precipitation of less soluble Fe and Al oxides and hydroxides along Sandy Run before entering the lake, producing a high Mn water input into the reservoir. Concentrations of heavy metals in the sediments increased toward the dam area. Sequential extraction of metals in the sediments showed that the highest fractions of metals corresponded to the detrital fraction or eroded material from the watershed and metals associated with iron and manganese hydroxides. Heavy metals in the organic sediment fraction were low. Heavy metals from the AMD source, as well as sediments rich in heavy metals eroded from the watershed, were transported to the downstream dam area and stored at the bottom, producing the observed chemistry. Heavy metals in benthic waters also were sourced from the diffusion of ions from sediments and lake waters as variation in pH and redox conditions determined the flux at the sediment–water interface. Metal concentrations were measured within two deposit feeders, oligochaetes and chironomids, and compared to trends in physical metal concentration across the lake. For the four heavy metals with higher concentration in both benthic animals, the concentrations followed the trend: Fe?>?Al?>?Mn?>?Zn, which were similar to the bioavailable metals in the sediments rather than the pore or the benthic water where Mn was the most abundant heavy metal. Ingestion of sediment, not exposure to pore or benthic waters, appeared to be the main transfer mechanism for metals into the biota. Trends and patterns in animal metal concentrations across the lake were probably a complex process controlled by metabolic needs and metallic regulation and tolerance. Even when Mn was the highest concentration heavy metal in the pore waters, it was the lowest to bioconcentrate in the organisms. In comparison, Cd, the lowest concentration metal in the sediments, presented one of the highest bioaccumulation factors.     

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.     

Monitoring Metal Speciation in The rivers Meuse and Rhine Using DGT

Although a number of metal speciation methods are nowadays available, most water quality regulations are based on total metal concentrations. One of the main reasons for the ignorance of speciation is the lack of methods with potentiality for monitoring. Conditions that have to be met by such speciation methods are: simple performance, robust and sufficiently accurate. In this study the potential for monitoring purposes of Diffusive Gradients in Thin films (DGT) is investigated as part of a European project for sensor development for routine prediction of metal biouptake in natural waters. Performance characteristics of DGT have been assessed in experiments under controlled laboratory conditions and during in situ application over 4–9 months under different hydrological conditions in the rivers Meuse and Rhine. Results have been worked out for Cu, Ni and Pb. The study shows that DGT has sufficient potential as a robust tool in routine monitoring to observe trends in water quality. However, it appears that during in situ application of DGT the measurement uncertainty of the results is much larger than under laboratory conditions. The increase in measurement uncertainties will partially be due to uncertainties in some as constant considered factors in the calculation of the DGT concentration. For Cu and Ni, the average values for the reproducibility in the rivers Meuse and Rhine appeared to be 28% and 17%, respectively, whereas under laboratory conditions the reproducibilities for both metals were better than 10%. In the speciation of Cu, Ni and Pb in the rivers Meuse and Rhine, the labile fraction, determined using DGT, decreased in the series Ni, Cu, Pb. The ratio of the non-labile and labile fractions of the metals appeared to decrease with increasing content of Dissolved Organic Carbon (DOC).     

Effect of phosphorus competition on arsenic bioavailability in dry and flooded soils: comparative study using diffusive gradients in thin films and chemical extraction methods

Purpose

Phosphorus influence on arsenic bioavailability in soils and its toxicity to plants is widely recognized. This work compares competitive influence of P on As bioavailability in dry and flooded soils.

Materials and methods

Pot experiments were carried out in dry and flooded soils, respectively. Bioavailable As in soils was measured using diffusive gradients in thin films (DGT), soil solution concentration, and three single chemical extraction methods.

Results and discussion

P concentration at 50 mg/kg promoted wheat growth in dry soil. At concentrations above 50 mg/kg, P competition inhibited wheat growth and enhanced As toxicity. In flooded soil, the rice height and biomass decreased with the increase of P addition. P concentrations above 800 mg/kg were lethal to the rice. The content of As absorbed by wheat and rice roots as well as shoots increased with the increase of P concentration. The bioavailability of As in wheat- and rice-grown soils, determined by all methods, also increased with the increase of P concentration. The correlation analysis between the bioavailable As measured by the all three methods and the content of As in plants showed a significant positive correlation. The Pearson correlation coefficient for the DGT method was higher comparing to all other methods. DGT-induced fluxes in soils (DIFS) modeling further showed sharp decreases of T_c (the characteristic time to reach equilibrium between available solid As pool and soil solution As from DGT perturbation) and increases of desorption and adsorption rate constants (k₁ and k_?1) of As in P-amended soils, reflecting that the kinetic release of As from available solid As pools became much easy from P competition.

Conclusions

P competition in both dry and flooded soils could significantly increase bioavailability of As and further increase its toxicity. Competition effect was more pronounced in flooded soil. DGT is a more accurate method for As bioavailability evaluation in both dry and flooded soils.

     

A new sediment contact assay to assess particle-bound pollutants using zebrafish (<Emphasis Type="Italic">danio rerio</Emphasis>) embryos

Goal, Scope and Background. Based on a bioassay battery covering only primary producers and consumers as well as degraders, the potential ecological hazard of sediments to vertebrates cannot be estimated comprehensively. Therefore, there is an urgent need to develop and standardize integrated vertebrate-based test systems for sediment investigation strategies. Whereas vertebratebased in vitro systems have frequently been used for the investigation of aqueous samples, there is a significant lack of whole sediment assays. Thus, the purpose of the present study was: (1) to develop a rapid and reliable, but comprehensive method to investigate native sediments and particulate matters without preceding extraction procedures; (2) to compare the hazard potential of solid phase sediments to the effects of corresponding pore waters and organic extracts in order to characterize the bioavailability of the particle-bound pollutants; and (3) to relatively evaluate the embryotoxic effects of sediments from the catchment areas of the rivers Rhine, Neckar and Danube. Methods (or Main Features).  To investigate the toxicity of sediment samples on vertebrates, the standard embryo toxicity test with the zebrafish (Danio rerio; Hamilton-Buchanan 1922) according to DIN 38415-6 was modified with respect to exposure scheme and toxicological endpoints. Sediments from the catchment area of the Neckar River were assessed using pore waters, acetonic extracts and native sediments in order to get inside into the potential bioavailability of particle-bound pollutants. A comprehensive test protocol for the investigation of native sediments in the embryo toxicity test with the zebrafish is presented. Results and Discussion.  The fish embryo assay with Danio rerio can be carried out with both aqueous and organic sediment extracts as well as native (whole, solid phase) sediment samples. Elongation of exposure time from 48 to up to 196 h significantly increased the mortality. Using the fish egg assay with native sediments, a broad range of embryotoxic effects could be elucidated, including clear-cut dose-response curves for the embryotoxic effects of contaminated sediments; in contrast, absence of embryotoxic effects could be demonstrated even for the highest test concentrations of unpolluted sediments. With native sediments, embryotoxicity was clearly higher than with corresponding pore waters, thus corroborating the view that — at least for fish eggs — the bioavailability of particle-bound lipophilic substances in native sediments is higher than generally assumed. The relative ranking of sediment toxicity was identical using both native sediments and sediment extracts, EC₂₀ values of the latter, however, being eight time lower higher than with the native sediments. A comparison of the embryo toxic effects of samples from the Neckar area with locations along the Rhine and Danube rivers elucidated a broad range of results, thus indicating different levels of contamination. Conclusions.  A modified protocol of the zebrafish embryo test allows the assessment of sediment toxicity in both aqueous extracts and native sediments. The isolated investigation of pore waters may result in a clear-cut underestimation of the bioavailability of lipophilic particle-bound substances (as determined by native sediments). Recommendations and Perspectives.  The zebrafish embryo test with native (whole, solid phase) sediments appears very promising for the evaluation of the bioavailable fraction of lipophilic particle-bound substances and can therefore be recommended for the evaluation of vertebrate toxicity in tiered sediment test strategies and dredging directives such as the HABAB-WSV. Whereas acetone extracts may be tested as a rough estimation of embryotoxicity, native sediment samples will provide a more comprehensive and realistic insight into the bioavailable hazard potential     

Assessing metal bioaccumulation from estuarine sediments: comparative experimental results for the polychaete Arenicola marina

Purpose

The purpose of this paper is to compare three approaches for providing information on the bioaccumulation potential of metals from contaminated sediments to the deposit-feeding polychaete Arenicola marina.

Materials and methods

We present metal (Ag, As, Cd, Cu, Pb and Zn) bioaccumulation results from field-collected sediments quantified through direct measurements of bioaccumulated concentrations in A. marina over a period of 30 days under controlled laboratory exposures and compare these results with bioaccumulated metal concentrations in field-collected organisms from the same sites of collection of the sediments used in the laboratory exposures. For the metals for which model parameters are available (Ag, As, Cd and Zn), we also compare these results with biodynamic model predictions. We considered three UK estuaries characterised by a well-reported history of trace metal contamination and bioavailability in addition to the (control) site of collection of the worms.

Results and discussion

The results from laboratory-exposed organisms showed that the standard 28-day exposure duration may be adequate to identify the potential for metal bioaccumulation in this polychaete at the sites considered here. However, the time course of bioaccumulated concentrations and the comparison with measured concentrations in field-collected worms show that a steady state has not been reached, confirming the need for extended exposure periods. The worms showed symptoms of stress in feeding and growth during the initial 10 days of exposure and subsequent partial recovery during the following 20 days, suggesting that stress was not always caused by sediment contamination but that it was likely associated with handling and acclimation. At this last stage of the exposure, a generalised biodynamic model was used to provide estimates of bioaccumulated metal concentrations and net accumulation rates in worms.

Conclusions

The results of this study highlight the number of factors that should be considered for the interpretation of bioaccumulated metal concentrations in A. marina under laboratory exposures for contaminated sediment assessment, factors that appear to be common to most deposit-feeding polychaetes. A general biodynamic model proved to be a cost-effective method for an initial estimation of the extent and pattern of metal bioaccumulation under specified exposure conditions.     

Mercury Concentration and Monomethylmercury Production in Sediment: Effect of Dredged Sediment Reuse on Bioconcentration for Ragworms

The effect of dredged sediment reuse on the production and bioconcentration of monomethylmercury (MMHg) was investigated by examining sediments and ragworms found in dredge material banks and surrounding sites in the Venice Lagoon, Italy. Total Hg concentrations in the surface 20 cm of sediments were higher in the banks than in the surrounding sites, but MMHg concentrations were similar, which suggests reduced MMHg production in the banks. Monomethylmercury content in ragworms was significantly lower (p?<?0.05) in the banks than in the surrounding sites. In pore water, concentrations of both sulfate and Fe decreased with depth in the upper 20 cm of the dredge banks. In contrast, sulfate concentrations were constant with depth and large amounts of dissolved Fe occurred in the upper 20 cm of sediments of surrounding sites. Continuous sulfate reduction and possible precipitation of iron sulfide may decrease the production and bioconcentration of MMHg in the dredge material banks compared to the surrounding sites. Overall, the production of MMHg in sediments and its bioconcentration in benthic organisms were connected to the process of sediment diagenesis of organic matter through the control of pore water and sediment geochemistry involving iron and sulfur.     

Measuring bioavailable trace metals by diffusive gradients in thin films (DGT): soil moisture effects on its performance in soils

Conventional methods of measuring labile chemical species of trace metals in soil solutions, such as chemical competition following centrifuging, are inadequate if the speciation changes during sampling and extraction. A new technique, diffusive gradients in thin films (DGT), measures labile species of trace metals in natural waters and sediments in situ. A well-defined diffusive gel layer distinguishes it from other resin-based techniques. It perturbs the soil in a controlled way by introducing an in situ local sink for metal ions. Resulting fluxes to the device are quantitatively measured, allowing assessment of re-supply kinetics and in some cases measurement of in situ soil solution concentrations. We used DGT to measure fluxes of Cd, Co, Cu, Ni, Pb and Zn in a sludge-treated soil at various moisture contents (27–106%). Replicate measurements showed that the precision of DGT-measured fluxes was within 10%. For moisture contents exceeding the field capacity (42%), the DGT response reflected soil water concentrations. At smaller moisture contents, changes related to tortuosity and dilution were reflected in the measurements. This technique has the potential for in situ measurements in the field where it should provide quantitative flux data on individual soils and provide a good surrogate for bioavailable metal.     

A geochemical analytical approach for the evaluation of heavy metal distribution in lagoon sediments

Background, Aim, and Scope  Italian lagoon environments are of great importance due either to their frequency and distribution along the coasts or to their management. Agriculture, urban and industrial activities in lagoon catchments can be sources of heavy metal (HM) pollution by direct waste dumping, atmospheric deposition of fumes or, simply, as a consequence of a lack of natural water recharge. HM concentration in lagoon sediments is a tool of HM monitoring in the surrounding environment. Application of sequential extraction procedures (SEP) to sediments makes it possible to study the HM distribution among the main geochemical phases and to assess their potential mobilization as a consequence of environmental condition variations. In the present study, the three-step SEP (0.11 m HOAc; 0.1 m NH₂OH·HCl; 8.8 m H₂O₂ and then 1 m NH₄OAc), developed by the Measurement and Testing Programme of the European Commission (BCR), was combined with information on the chemical and mineralogical properties of the sediments in order to assess the level and risk of mobility of HM (Cu, Cr, Cd, Pb, Ni, Zn) in sediments from the Fusaro volcanic coastal lagoon of southern Italy. The effect of sediment air drying and physico-chemical properties on the metal distribution in various geochemical forms and fractions was considered. Materials and Methods  Surface (5 cm depth) sediment samples were collected from twenty-one sites on the Fusaro lagoon. Moisture, pH, organic carbon, carbonates, particle-size distribution and HM total content were determined on the dried sediment samples. The mineralogy of the clay fraction was determined at room temperature on random and oriented samples. The different forms of Al, Si and Fe in the bulk sediment (< 2 mm) were analyzed after oxalate, dithionite-citrate and pyrophosphate extractions. The BCR-SEP was used to fractionate trace element chemical forms in nine selected sediment samples. Effects of sediment air-drying on HM fractionation were analyzed. Results  Middle (Cu, Cr) and low (Cd, Pb, Zn) concentrations of heavy metals in sediment samples from the deeper central part of the lagoon were observed. Cadmium resulted in mainly being associated with carbonate forms (∼60%), whereas Cr and Ni occurred primarily as residual mineral phases (>50%). Zn appeared uniformly distributed among the main geochemical forms. Considerable presence of Cr, Cu and Pb was found in the oxidizable fraction (∼50%), indicating organic matter and/or sulphides major sinks for these metals. Differences of heavy metal distribution among sediment samples were observed, depending on the total metal content and on sediment properties. Modifications in metal speciation induced by sediment air drying mainly consist of a transfer of the actual and potentially mobile fractions towards immobile fractions (mineral residue) by oxidation and formation of Fe and Mn oxides. Discussion  Both total content and sequential extraction results did not show an environmental critical situation: the only possible risk, associated with heavy element mobility, could occur in consequence of a drastic pH and redox equilibria variation at the water-sediment interface. Conclusions  Despite all limitations, the BCR-SEP combined with information on the chemical and mineralogical properties of the sediment solid matrix provides a valuable approach to describe the risks related to the potentially toxic HM occurring in sediments (in this paper the case of the Fusaro lagoon is examined). HM distribution among the sequentially extracted geochemical forms is affected by sediment properties, such as pH (Zn), clay (Cd), Fe easily reducible oxides (Pb) and organic matter (Cu) content. Recommendations  Political managers, usually facing limitations of time and resources, have to optimize the cognitive phases, selecting the most useful information to make ‘effective and correct decisions’ in the environmental field. Therefore, although conscious of the limits of the adopted quality assessment, we believe it represents a good compromise between time and resource availability (i.e. type and quality of information). Outlook  The complementary use of the simple and rapid European fractionation scheme with information on the chemical and mineralogical properties of the sediments provides more awareness about the nature of the sediment components involved and offers a more reliable way for studying HM speciation in sediments.     

Effects of compaction on soil hydraulic properties,penetration resistance and water flow patterns at the soil profile scale

The aim of this study was to quantify the effects of compaction on water flow patterns at the soil profile scale. Control and trafficked plots were established in field trials at two sites. The trafficked treatment was created by four passes track‐by‐track with a three‐axle dumper with a maximum wheel load of 5.8 Mg. One year later, dye‐tracing experiments were performed and several soil mechanical, physical and hydraulic properties were measured to help explain the dye patterns. Penetration resistance was measured to 50 cm depth, with saturated hydraulic conductivity (K_s), bulk density, and macroporosity and mesoporosity being measured on undisturbed soil cores sampled from three depths (10, 30 and 50 cm). Significant effects of the traffic treatment on the structural pore space were found at 30 cm depth for large mesopores (0.3–0.06 mm diameter), but not small mesopores (0.06–0.03 mm) or macroporosity (pores > 0.3 mm). At one of the sites, ponding was observed during the dye‐tracing experiments, especially in the trafficked plots, because of the presence of a compacted layer at plough depth characterized by a larger bulk density and smaller structural porosity and K_s values. Ponding did not induce any preferential transport of the dye solution into the subsoil at this site. In contrast, despite the presence of a compacted layer at 25–30 cm depth, a better developed structural porosity in the subsoil was noted at the other site which allowed preferential flow to reach to at least 1 m depth in both treatments.     

Phosphorus availability of sewage sludge‐based fertilizers determined by the diffusive gradients in thin films (DGT) technique

The plant‐availability of phosphorus (P) in fertilizers and soil can strongly influence the yield of agricultural crops. However, there are no methods to efficiently and satisfactorily analyze the plant‐availability of P in sewage sludge‐based P fertilizers except by undertaking time‐consuming and complex pot or field experiments. We employed the diffusive gradients in thin films (DGT) technique to quantify the plant P availability of various types of P fertilizers with a novel focus on sewage sludge‐based P fertilizers. Mixtures of fertilizer and soil were incubated for 3 weeks at 60% water holding capacity. DGT devices were deployed at the beginning of the incubation and again after 1, 2, and 3 weeks. Two weeks of incubation were sufficient for the formation of plant‐available P in the fertilizer/soil mixtures. In a pot experiment, the DGT technique predicted maize (Zea mays L.) biomass yield and P uptake significantly more accurately than standard chemical extraction tests for P fertilizers (e.g ., water, citric acid, and neutral ammonium citrate). Therefore, the DGT technique can be recommended as a reliable and robust method to screen the performance of different types of sewage sludge‐based P fertilizers for maize cultivation minimizing the need for time‐consuming and costly pot or field experiments.     

Effects of Underground Pore Fissures on Soil Erosion and Sediment Yield on Karst Slopes

Underground pore fissure is one of common ways of soil leakage, and the soil loss in underground pore fissure would aggravate the development of rocky desertification in karst areas. A designed steel tank with varied underground pore fissure degrees was used to measure how underground pore fissure affected soil erosion and sediment yield on karst bare slope. We found that sediment yield rates and its distribution ratios obviously differed between the surface and underground. Surface sediment yield rate greatly responded to rainfall intensity conditions, while underground sediment yield rate rarely changed. Both bed rock bareness and underground pore fissure degree had an insignificant effect on both surface and underground sediment yield rate, but the former greatly influenced sediment distribution between the surface and underground. With increasing of bed rock bareness rate, both the average surface and underground sediment yield rates first increased and then decreased. The later posed an effect on underground sediment yield rate, which increased with increase of underground pore fissure degree. With increase of underground pore fissure degree, critical rainfall intensity for producing surface sediment would increase from 0.8–1.3 mm min⁻¹ to 1.3–2.0 mm min⁻¹. The results provide a mechanistic understanding of how underground pore fissure affects soil erosion and sediment production. Copyright © 2017 John Wiley & Sons, Ltd.