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.

Repurposing spent filter sand from iron and manganese removal systems as an adsorbent for treating arsenic contaminated drinking water.

Waterworks which utilise river bank filtration water sources often have to apply aeration and sand filtration to remove iron and manganese during the drinking water treatment process. After some time, the sand becomes saturated and the spent filter sand (SFS) must be disposed of and replaced. In order to valorize this waste stream, this paper investigates the reuse of SFS as an adsorbent for the treatment of arsenic contaminated drinking water. The arsenic removal performance of SFS is compared with two synthetic iron oxide coated sands (IOCS). The sorbents were first characterized by SEM, EDS, BET specific surface area, and point of zero charge (pHpzc) measurements, and then investigated under a variety of conditions. The surface of the SFS was revealed to be coated with iron manganese binary oxide. The Freundlich model best described the isotherm experiment data, indicating a non monolayer adsorption model for arsenic adsorption on the three IOCS investigated. As(III) and As(V) removals were negatively effected by the presence of PO43- and HA anions as they competed with the arsenic species for adsorption sites. However, given the status of SFS as a waste material, the results obtained in this paper suggest it may be successfully reused as a very economically and environmentally sustainable solution for small waterworks requiring both As(V) and As(III) removal during drinking water treatment.

Synthesis, characterization and application of magnetic nanoparticles modified with Fe-Mn binary oxide for enhanced removal of As(III) and As(V).

Arsenic contamination of drinking water sources is a widespread global problem. Of the As species commonly found in groundwater, As(III) is generally more mobile and toxic than As(V). In this work, magnetic nanoparticles (MNp) modified with Fe-Mn binary oxide (MNp-FeMn) were synthesized in order to develop a low cost adsorbent with high removal efficiency for both arsenic species which can be readily separated from water using a magnetic field. MNp-FeMn were characterized using different techniques including SEM/EDS, XRD and BET analysis. Adsorption of As(III) and As(V) on MNp-FeMn was studied as a function of initial arsenic concentration, contact time, pH, and coexisting anions. The BET specific surface area of MNp-FeMn was 109 m2/g and maghemite (γ-Fe2O3) was the dominant precipitated phase. The adsorption rate of As(III) and As(V) on MNp-FeMn was controlled by surface diffusion. FTIR analysis confirms that surface complexation through ligand exchange was the main mechanism for As(III) and As(V) removal on MNp-FeMn, with As(III) conversion to As(V) occurring on the adsorbent surface. The maximal adsorption capacity qmax of MNp for As(III) (26 mg/g) was significantly improved after modification with Fe-Mn binary oxide (56 mg/g), while qmax for As(V) was 51 and 54 mg/g, respectively. PO43-, SiO32- and CO32- reduced As(III) and As(V) uptake at higher concentrations. MNp-FeMn can be easily regenerated and reused with only a slight reduction in adsorption capacity. The high oxidation and sorption capacity of MNp-FeMn, magnetic properties and reusability, suggest this material is a highly promising adsorbent for treatment of arsenic contaminated groundwater.

Impact of hydrochar and biochar amendments on sorption and biodegradation of organophosphorus pesticides during transport through Danube alluvial sediment.

This work investigates the transport behaviour of selected organophosphorus pesticides, OPPs (chlorpyrifos, CP; chlorpyrifos-methyl, CPM; chlorfenvinphos, CF) through Danube alluvial sediment in the presence of hydrochars and biochars. The investigated hydrochar, obtained at three different temperatures (180 °C, 200 °Cand 220 °C), originated from sugar beet shreds (SBS) and Miscanthus×giganteus (MIS). Results are described by conventional advective-dispersive equation (ADE). Retardation coefficients (Rd) for all OPPs were in the range 6.2-16. Biodegradation was 4.15 and 1.80 for CPM and CP, respectively, while for CF biodegradation did not occur. The addition of carbon rich materials increases retardation of all OPPs in the range from 4 to 18 times depending on the material. Column experiment results indicated that biodegradation of OPPs occurred (up to λ = 13). In order to confirm that biodegradation occurred in the column experiments, we isolated OPPs degrading microorganisms for the first time from the alluvial sediment. A strain capable of degrading CP and CPM was isolated and identified as Bacillus megaterium BD5 based on biochemical properties, MALDI TOF and 16S rRNA analysis (99.54% identity). The results demonstrate that hydrochars, biochars and isolated degrading bacteria may be effective agents for reducing the mobility of or removing OPPs in contaminated soils or sediments.

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.

Priority substances in sediments of the "Carska Bara" special nature reserve, a natural scientific research area on the UNESCO list.

Surface sediments were subject to systematic long-term monitoring (2002-2014) in the Republic of Serbia (Province of Vojvodina). Eight heavy metals (Ni, Zn, Cd, Cr, Cu, Pb, As and Hg), mineral oils (total petroleum hydrocarbons), 16 EPA PAHs, selected pesticides and polychlorinated biphenyls (PCB) were monitored. As part of this research, this paper presents a sediment contamination spatial and temporal trend study of diverse pollution sources and the ecological risk status of the alluvial sediments of Carska Bara at three representative sampling sites (S1S3), in order to establish the status of contamination and recommend substances of interest for more widespread future monitoring. Multivariate statistical methods including factor analysis of principal component analysis (PCA/FA), Pearson correlation and several synthetic indicators were used to evaluate the extent and origin of contamination (anthropogenic or natural, geogenic sources) and potential ecological risks. Hg, Cd, As, mineral oils and PAHs (dominated by dibenzo(a,h)anthracene and benzo(a)pyrene, contributing 85.7% of the total) are derived from several anthropogenic sources, whereas Ni, Cu, Cr and Zn are convincingly of geogenic origin, and exhibit dual origins. Cd and Hg significantly raise the levels of potential ecological risk for all sampling locations, demonstrating the effect of long-term bioaccumulation and biomagnification. Pb is isolated from the other parameters, implying unique sources. This research suggests four heavy metals (Zn, Cr, Cu and As) and dibenzo(a,h)anthracene be added to the list of priority pollutants within the context of the application of the European Water Framework Directive (WFD), in accordance with significant national and similar environmental data from countries in the region.

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.