Comparing biochar and hydrochar for reducing the risk of organic contaminants in polluted river sediments used for growing energy crops.

In Europe alone, >200 million m3 of river sediments are dredged each year, part of which are contaminated to such an extent that they have to be landfilled. This study compares the use of biochar and hydrochar for the remediation of sediment contaminated with pentachlorobenzene, hexachlorobenzene, lindane, trifluralin, alachlor, simazine, and atrazine with the motivation to make sediments contaminated by such priority substances usable as arable land for growing energy crops. Biochar and hydrochar originating from Miscanthus giganteus and Beta vulgaris shreds were compared for their potential to reduce contaminant associated risk in sediments. Specifically, by investigating the effects of sorbent amendment rate (1, 5, and 10 %) and incubation time (14, 30, and 180 d) on contaminant bioaccessibility, toxicity to the bacteria Vibrio fischeri, as well as toxicity and plant uptake in Zea mays. Biochar reduced contaminant bioaccessibility up to five times more than hydrochar. The bioaccessibility of contaminants decreased up to sevenfold with increasing incubation time, indicating that the performance of carbonaceous sorbents may be underestimated in short-term lab experiments. Biochar reduced contaminants toxicity to Vibrio fischeri, whereas hydrochar was itself toxic to the bacteria. Toxicity to Zea mays was determined by contaminant bioaccessibility but also sorbent feedstock with cellulose rich Beta vulgaris based sorbents exhibiting toxic effects. The plant uptake of all contaminants decreased after sorbent amendment.

Current State and Future Perspectives of Carbon-Based Materials in the Environment: Fate and Application.

BACKGROUND: Environmental pollution has been a recognized problem for human health and the ecosystem. Remediation is usually costly and time-consuming, so researchers' attention has been drowning to develop and use new materials. This review aims to summarize the recent development of carbon-based materials used for environmental management. METHODS: We conducted a detailed analysis of available literature based on the Web of Science database. In the third part of the manuscript are given some of the recent patents on carbon-based materials. The corresponding papers were carefully evaluated. RESULTS: More than one hundred and ninety papers were included in section literature. Based on the available literature it an increasing trend in carbon-based material usage can be observed. These materials are used in resolving environmental issues: adsorbents in water and wastewater treatment; precursor of catalysts, soil improvement, waste management, climate change mitigation, electrochemical energy storage and soil remediation adsorption processes. Although it is a mainly new approach considered as environmentally friendly, there are finding, observation, negative aspects, and conclusion that must be taken into consideration. CONCLUSION: The findings of this review confirm that many factors must be considered when carbon- based materials are used. At the same time, this review aims to emphasize development trends in providing a useful guide to design and fabricate high-efficiency and low-cost carbon materials.

Ex situ remediation of sediment from Serbia using a combination of electrokinetic and stabilization/solidification with accelerated carbonation treatments.

The application of three simple and cost-effective technologies for ex situ remediation of the sediment of Begej River in Serbia is presented in this paper. In the first step, conventional electrokinetic treatment (EK) was carried out to reduce the amount of contaminated sediment and enhance the accumulation of metals. Subsequently, stabilization/solidification (S/S) treatment was applied to the remaining portion of polluted sediment to immobilize the accumulated metals. At the same time, the influence of accelerated carbonation on the effectiveness of the treatment was evaluated. The immobilizing agents used in this study included bio ash produced by combustion of wheat and soy straw mixture and bio ash derived from molasses incineration. After the treatments, the risk assessment was performed by using the sequential extraction procedure (SEP) and TCLP and DIN 3841-4 S4 leaching tests. The results obtained after the EK treatment revealed a reduction in the amount of polluted sediment to a half. Leaching tests and SEP performed on S/S mixtures after a 28-day maturation period indicated that accelerated carbonation decreased the mobility of critical metals, especially in wheat and soy straw mixtures. Moreover, based on the leaching tests, all prepared mixtures were categorized as non-hazardous and safe for disposal according to the relevant Serbian regulations. The newly developed method that combines EK and S/S treatments with the addition of accelerated carbonation produced reduced volumes of stabilized sediment which is safe for disposal.

Growth, physiology, and phytoextraction potential of poplar and willow established in soils amended with heavy-metal contaminated, dredged river sediments.

Phytotechnologies have been used worldwide to remediate and restore damaged ecosystems, especially those caused by industrial byproducts leaching into rivers and other waterways. The objective of this study was to test the growth, physiology, and phytoextraction potential of poplar and willow established in soils amended with heavy-metal contaminated, dredged river sediments from the Great Backa Canal near Vrbas City, Serbia. The sediments were applied to greenhouse-grown trees of Populus deltoides Bartr. ex Marsh. clone 'Bora' and Salix viminalis L. clone 'SV068'. Individual pots with trees previously grown for two months were amended with 0, 0.5 and 1.0 kg of sediment containing 400 mg Cr kg-1, 295 mg Cu kg-1, 465 mg Zn kg-1, 124 mg Ni kg-1, 1.87 mg Cd kg-1, and 61 mg Pb kg-1. Following amendment, trees were grown for two seasons (i.e., 2014, 2015), with coppicing after the first season. In addition to growth parameters, physiological traits related to the photosynthesis and nitrogen metabolism were assessed during both growing seasons. At the end of the study, trees were harvested for biomass analysis and accumulation of heavy metals in tree tissues and soils. Application of sediment decreased aboveground biomass by 37.3% in 2014, but increased height (16.4%) and leaf area (19.2%) in 2015. Sediment application negatively impacted the content of pigments and nitrate reductase activity, causing them to decrease over time. Generally, the effect of treatments on growth was more pronounced in poplars, while willows had more pronounced physiological activity. Accumulation patterns were similar to previously-published results. In particular, Zn and Cd were mostly accumulated in leaves of both poplar and willow, which indicated successful phytoextraction. In contrast, other metals (e.g., Cr, Ni, Pb, Cu) were mostly phytostabilized in the roots. Differences in metal allocation between poplar and willow were recorded only for Cu, while other metals followed similar distribution patterns in both genera. Results of this study indicated that the composition of heavy metals in the sediments determined the mechanisms of the applied phytoremediation technique.

Lindane and hexachlorobenzene sequestration and detoxification in contaminated sediment amended with carbon-rich sorbents.

Sediment represents a sink for toxic and persistent chemicals such as hexachlorobenzene (HCB) and lindane (γ-HCH). This paper investigates the possibility of reducing the risks associated with the presence of these pollutants in sediments by amending the sediment with carbon-rich materials (activated carbon (AC) and humus (HC)) to sequester the contaminants and render them biologically unavailable. The effects of the dose and contact time between the sediment and the carbon-rich amendments on the effectiveness of the detoxification are estimated. Four doses of carbon-rich amendments (0.5-10%) and four equilibration contact times (14-180 days) were investigated. Results have shown that the bioavailable fraction of γ-HCH and HCB decreased significantly in comparison to the unamended sediment. Regarding the AC amendments, almost 100% for both compounds; and for HC amendments around 95% for γ-HCH, and 75% for HCB. Aging caused further reductions in the bioavailable fraction, compared to the untreated sediment. Phytotoxicity tests showed that Zea mays accumulated significantly higher amount of γ-HCH and HCB from unamended sediment, comparing to Cucurbita pepo and Lactuca sativa. Toxicity of HC and AC amended sediment assessed by Vibrio fischeri luminescence inhibition test and by measuring Zea mays germination and biomass yield was significantly reduced in the amended sediment samples. γ-HCH and HCB accumulation in the Zea mays biomass in the unamended sediment were a significantly higher than in the all HC and AC amended sediment. Both sorbents show potential to be used as remediation agents for organically contaminated sediment, but AC exhibited the better performance.

State of the art and future challenges for polycyclic aromatic hydrocarbons is sediments: sources, fate, bioavailability and remediation techniques.

Polycyclic aromatic hydrocarbons (PAHs) are amongst the most abundant contaminants found in the aquatic environment. Due to their toxicity and carcinogenicity, their sources, fate, behaviour, and cleanup techniques have been widely investigated in the last several decades. When entering the sediment-water system, PAH fate is determined by particular PAH and sediment physico-chemical properties. Most of the PAHs will be associated with fine-grained, organic-rich, sediment material. This makes sediment an ultimate sink for these pollutants. This association results in sediment contamination, and in this manner, sediments represent a permanent source of water pollution from which benthic organisms may accumulate toxic compounds, predominantly in lipid-rich tissues. A tendency for biomagnification can result in critical body burdens in higher trophic species. In recent years, researchers have developed numerous methods for measuring bioavailable fractions (chemical methods, non-exhaustive extraction, and biomimetic methods), as valuable tools in a risk-based approach for remediation or management of contaminated sites. Contaminated sediments pose challenging cleanup and management problems, as conventional environmental dredging techniques are invasive, expensive, and sometimes ineffective or hard to apply to large and diverse sediment sites. Recent studies have shown that a combination of strategies including in situ approaches is likely to provide the most effective long-term solution for dealing with contaminated sediments. Such in situ approaches include, but are not limited to: bioaugmentation, biostimulation, phytoremediation, electrokinetic remediation, surfactant addition and application of different sorbent amendments (carbon-rich such as activated carbon and biochar) that can reduce exposure and limit the redistribution of contaminants in the environment.

Potential for anaerobic treatment of polluted sediment.

Due to the anaerobic nature of aquatic sediments, the anaerobic treatment of sediments utilizing already present microflora represents an interesting treatment option. Contaminated sediment can contain a variety of organic contaminants, with easily degradable organics usually present in the higher amounts, along with traces of specific organic pollutants (total petroleum hydrocarbons and polycyclic aromatic hydrocarbons). This study applies a comprehensive approach to contaminated sediment treatment which covers all the organic contaminants present in the sediment. The aim of this study was to (1) evaluate the anaerobic treatment of aquatic sediment highly loaded with easily degradable organics via determination of potential biogas and methane production, and (2) assess possibilities of using anaerobic treatment for the degradation of specific organic pollutants in order to reduce the risks posed by the sediment. In order to promote the methanogenic conditions of the indigenous microflora in the sediment, the addition of co-substrates acetate and glucose was investigated. The results, expressed as mL biogas produced per volatile solids content in sediment (VSadded) indicate that the addition of the co-substrate has a significant impact on biogas production potential (58.7 and 55.1 mL/g VSadded for acetate and glucose co-substrate addition respectively, and 14.6 mL/g VSadded for the treatment without co-substrate addition). Theoretical biochemical methane potential was assessed by Gompertz model and Chemical oxygen demand model. The Gompertz model fit better for all the applied treatments, and was capable of predicting the final productivity of biogas and methane in the first 30 days with a relative error of less than 14%. From the aspects of specific organic pollutants, total petroleum hydrocarbon degradation was promoted by co-substrate addition (degradations of 75% and 60% achieved by acetate and glucose co-substrate addition, compared to 45% for the treatment without co-substrate addition). Polycyclic aromatic hydrocarbons were reduced by significant amounts (84-87%) in all the applied treatments, but the addition of co-substrate did not further improve their degradation.

The role of organic matter and clay content in sediments for bioavailability of pyrene.

Evaluation of the bioavailable fractions of organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) is extremely important for assessing their risk to the environment. This available fraction, which can be solubilised and/or easily extracted, is believed to be the most accessible for bioaccumulation, biosorption and/or transformation. Sediment organic matter (OM) and clay play an important role in the biodegradation and bioavailability of PAHs. The strong association of PAHs with OM and clay in sediments has a great influence not only on their distribution but also on their long-term environmental impact. This paper investigates correlations between bioavailability and the clay and OM contents in sediments. The results show that OM is a better sorbent for pyrene (chosen as a model PAH) and that increasing the OM content reduces the bioavailable fraction. A mathematical model was used to predict the kinetic desorption, and these results showed that the sediment with the lowest content of OM had an Ffast value of 24%, whereas sediment with 20% OM gave a value of 9%. In the experiments with sediments with different clay contents, no clear dependence between clay and rate constants of the fast desorbing fractions was observed, which can be explained by the numerous possible interactions at the molecular level.

A chemical and microbiological characterization and toxicity assessment of the Pancevo industrial complex wastewater canal sediments, Serbia.

The wastewater canal Vojlovica of the Pancevo industrial area, Serbia, is the main collector of the effluents from the local industrial complex. The canal is directly connected to the Europe's second largest river, the Danube. Here, we present a chemical and microbiological analysis of the sediment in order to determine the fate of pollutants over the years, as well as its current condition. Dry matter, clay and organic matter content, a Kjeldahl ammonia, phosphorus, metals, and polychlorinated biphenyls as well as polycyclic aromatic hydrocarbons concentrations were measured. Microbiological analysis included heterotrophic and oil-degrading bacterial counts, isolation of the phenanthrene-degrading bacteria, and identification of cyanobacteria. Generally, in comparison to the results from previous studies, concentrations of the measured pollutants have been in a decline. Specifically, the metal and polycyclic aromatic hydrocarbon concentrations were reduced whereas microbial counts and toxicity tests did not indicate significant pollution. The obtained results are probably a consequence of an improved wastewater treatment and microbial degradation of pollutants.

Assessment of the bioavailability and phytotoxicity of sediment spiked with polycyclic aromatic hydrocarbons.

Large amounts of sediment are dredged globally every year. This sediment is often contaminated with low concentrations of metals, polycyclic aromatic hydrocarbons, pesticides and other organic pollutants. Some of this sediment is disposed of on land, creating a need for risk assessment of the sediment disposal method, to minimize the degradation of environmental quality and prevent risks to human health. Evaluating the available fractions of certain polycyclic aromatic hydrocarbons is very important, as in the presence of various organisms, they are believed to be easily subject to the processes of bioaccumulation, biosorption and transformation. In order to determine the applicability of applying these methods for the evaluation of pollutant bioavailability in sediments, the desorption kinetics from the sediment of various polycyclic aromatic hydrocarbons in the presence of Tenax and XAD4 were examined over the course of 216 h. Changes in the PAH concentrations in dredged sediments using five different seed plants during a short time of period (10 days) were also followed. Using chemical extraction techniques with Tenax and XAD4, a time of around 24 h is enough to achieve equilibrium for all four PAHs. Results showed good agreement between the seed accumulation and PAH extraction methods with both agents. If we compare the two extraction techniques, XAD4 gave better results for phenanthrene, pyrene and benzo(a)pyrene, and Tenax gave better results for chrysene.

Trace level voltammetric determination of lead and cadmium in sediment pore water by a bismuth-oxychloride particle-multiwalled carbon nanotube composite modified glassy carbon electrode.

Two multiwalled carbon nanotubes-based composites modified with bismuth and bismuth-oxychloride particles were synthesized and attached to the glassy carbon electrode substrate. The resultant configurations, Bi/MWCNT-GCE and BiOCl/MWNT-GCE, were then characterized with respect to their physicochemical properties and electroanalytical performance in combination with square-wave anodic stripping voltammetry (SWASV). Further, some key experimental conditions and instrumental parameters were optimized; namely: the supporting electrolyte composition, accumulation potential and time, together with the parameters of the SWV-ramp. The respective method with both electrode configurations has then been examined for the trace level determination of Pb(2+) and Cd(2+) ions and the results compared to those obtained with classical bismuth-film modified GCE. The different intensities of analytical signals obtained at the three electrodes for Pb(2+) and Cd(2+) vs. the saturated calomel reference electrode had indicated that the nature of the modifiers and the choice of the supporting electrolyte influenced significantly the corresponding stripping signals. The most promising procedure involved the BiOCl/MWCNT-GCE and the acetate buffer (pH 4.0) offering limits of determination of 4.0 µg L(-1) Cd(2+) and 1.9 µg L(-1) Pb(2+) when accumulating for 120 s at a potential of -1.20 V vs. ref. The BiOCl/MWCNT electrode was tested for the determination of target ions in the pore water of a selected sediment sample and the results agreed well with those obtained by graphite furnace atomic absorption spectrometry.

Using chemical desorption of PAHs from sediment to model biodegradation during bioavailability assessment.

This work compares the biodegradation potential of four polycyclic aromatic hydrocarbons (PAH) (phenanthrene, pyrene, chrysene and benzo(a)pyrene, chosen as representatives of the 3, 4 and 5 ring PAHs) with their desorption from sediment by XAD4 resin and methyl-ß-cyclodextrin (MCD). The biodegradation study was conducted under various conditions (biostimulation, bioaugmentation and their combination). The results show that total PAH removal in all treatments except biostimulation gave similar results, whereby the total amount of PAHs was decreased by about 30-35%. The desorption experiment showed that XAD4 desorbed a greater fraction of phenanthrene (77% versus 52%), and benzo(a)pyrene (44% versus 25%) than MCD. The results for four ring PAHs were similar for both desorption agents (about 30%). Comparing the maximum biodegraded amount of each PAH with the rapidly desorbed XAD4 and MCD fraction, XAD4 was found to correlate better with biodegradation for the high molecular PAHs (pyrene, chrysene, benzo(a)pyrene), although it overestimated the availability of phenanthrene. In contrast, MCD showed better correlation with the biodegradation of low molecular weight PAHs.

Electrokinetic Treatment of Cr-, Cu-, and Zn-Contaminated Sediment: Cathode Modification.

Enhanced electrokinetic (EK) removal of Cr, Cu, and Zn from sediment by using original and modified integrated ion exchange (IIX™) cathodes was investigated. IIX cathode design and EK device process modifications were made to improve performance: separation of IIX cathode components (IIXS), combination of modified IIX cathode with pulsed electric field (IIXSP), and separation of IIX cathode components with addition of an anion exchange resin compartment (IIXA). After using the IIXSP, overall Cr, Cu, and Zn removal efficacies were significantly improved compared with the other treatments investigated. No improvements in overall Cr, Cu, and Zn removal efficacies were achieved by utilization of IIXA. Nevertheless, significant removal efficacies occurred at the anode region since distribution of the alkaline front was prevented. However, metal accumulation in the cathode region occurred. This was a consequence of metal cation complexation with Cl- released from the anion exchange resin that changed the direction of metal migration. Enhancing EK remediation of Cr-, Cu-, and Zn-contaminated sediment can be achieved by using a modified IIX cathode.

Influence of pH and ozone dose on the content and structure of haloacetic acid precursors in groundwater.

This study investigated the effects of pH (6-10) and ozone dose [0.4-3.0 mg O(3)/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85 ± 0.18 mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65 % fulvic and 14 % humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309 ± 15 µg/L). Ozonation at pH 6-10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65-90 % achieved using 3.0 mg O(3)/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH 10 (up to 68 % HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1 ± 6.0 µg/mg DOC in raw water to 152 ± 8 µg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH 10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.

Impact of hydrocarbon type, concentration and weathering on its biodegradability in soil.

The objective of this research was to investigate the impact of the hydrocarbon type and concentration, as well as the total effect of the natural weathering process to hydrocarbon biodegradability in sandy soil and the environment. In this experiment, sandy soil was separately contaminated with 0.5%, 1.0%, 2.0% and 3.5% of diesel and crude oils. Oil contaminated soil was taken from the Oil Refinery dumping sites after 9 years of weathering, and its concentration was adjusted to the above-mentioned levels. The biodegradation process was monitored by measuring CO(2), evolution rate, hydrocarbon degradation rate and dehydrogenase activity. The favourable concentration ranges for the soil contaminated with diesel oil were 1.0%, with concentrations at about 2.0% causing slightly adverse effects to CO(2) production which was overcome after 2 weeks, and with 3.5% diesel oil causing significant toxicity. For soil contaminated with crude oil, 2.0% was found to be optimum for effective biodegradation, with 3.5% crude oil also causing adverse effects to CO(2) production, although less so than the same concentration of diesel oil. No adverse effect was obtained for any concentration of the weathered oil, as after the weathering process, the remaining contaminants in the soil were mostly poorly degradable constituents like asphaltenes, resins etc. It has been proposed that such residual material from oil degradation is analogous to, and can even be regarded as, humic material. Due to its inert characteristics, insolubility and similarity to humic materials it is unlikely to be environmentally hazardous.

Correlation between the results of sequential extraction and effectiveness of immobilization treatment of lead- and cadmium-contaminated sediment.

The assessment of the quality of sediment from the Great Backi Canal (Serbia), based on the pseudo-total lead (Pb) and cadmium (Cd) content according to the corresponding Dutch standards and Canadian guidelines, showed its severe contamination with these two metals. A microwave-assisted BCR (Community Bureau of Reference of the Commission of the European Union) sequential extraction procedure was employed to assess their potential mobility and risk to the aquatic environment. Comparison of the results of sequential extraction and different criteria for sediment quality assessment has led to somewhat contradictory conclusions. Namely, while the results of sequential extraction showed that Cd comes under the high-risk category, Pb shows low risk to the environment, despite its high pseudo-total content. The contaminated sediment, irrespective of the different speciation of Pb and Cd, was subjected to the same immobilization, stabilization/solidification (S/S) treatments using kaolinite, montmorillonite, kaolinite-quicklime, montmorillonite-quicklime, fly ash, zeolite, or zeolite-fly ash combination. Semi-dynamic leaching tests were conducted for Pb- and Cd-contaminated sediment in order to assess the long-term leaching behavior of these metals. In order to simulate "worst case" leaching conditions, the semi-dynamic leaching test was modified using 0.014 M acetic acid (pH = 3.25) and humic acid solutions (20 mg TOC l-1) as leachants instead of deionized water. The effectiveness of S/S treatment was evaluated by determining diffusion coefficients (De) and leachability indices (LX). The standard toxicity characteristic leaching procedure (TCLP) was applied to evaluate the extraction potential of Pb and Cd. A diffusion-based model was used to elucidate the controlling leaching mechanisms. Generally, the test results indicated that all applied S/S treatments were effective in immobilizing Pb and Cd, and the treated sediments may be considered acceptable for "controlled utilization" based on LX values, irrespective of their different availability in the untreated samples. In the majority of samples, the controlling leaching mechanism appeared to be diffusion, which indicates that a slow leaching of Cd and Pb could be expected when the above S/S agents were applied. The TCLP results showed that all S/S samples were nonhazardous.