Reusable magnetite nanoparticles-biochar composites for the efficient removal of chromate from water.

Biochar (BC) and magnetite (Fe3O4) nanoparticles (MNP) have both received considerable recent attention in part due to their potential use in water treatment. While both are effective independently in the removal of a range of anionic metals from aqueous solution, the efficacy of these materials is reduced considerably at neutral pH due to decreased metal adsorption and MNP aggregation. In addition to synthetic metal oxide-biochar composites for use in treatment and remediation technologies, aggregates may also occur in nature when pyrolytic carbon is deposited in soils. In this study, we tested whether magnetite synthesized in the presence of biochar leads to increased removal efficiency of hexavalent chromium, Cr(VI), at the mildly acidic to neutral pH values characteristic of most natural and contaminated aqueous environments. To do so, magnetite nanoparticles and biochar produced from ground willow were synthesized to form composites (MNP-BC). Batch studies showed that MNP-BC markedly enhanced both adsorption and reduction of Cr(VI) from aqueous solution at acidic to neutral pH as compared to MNP and BC separately, suggesting a strong synergetic effect of hybridizing Fe3O4 with BC. Mechanistically, the Cr(VI) removal processes occurred through both adsorption and intraparticle diffusion followed by reduction to Cr(III). Synchrotron-based X-ray absorption spectroscopy analyses confirmed that Cr(VI) was reduced at the surface of MNP-BC, with electrons derived directly from both biochar and magnetite at low pH, while at near-neutral pH, biochar increased Cr(VI) reduction by inhibiting MNP aggregation. Extended X-ray absorption fine structure fitting results confirmed that the Cr(III) precipitates consist of Cr(OH)3 and chromite (Cr2FeO4) nanoparticles. Our results demonstrate that MNP-BC composites have great potential as a material for the treatment of chromate-containing aqueous solutions across a wide range of pH values, and provide information valuable broadly relevant to soils and sediments that contain biochar.

Characterization and implications of solids associated with hydraulic fracturing flowback and produced water from the Duvernay Formation, Alberta, Canada.

Public concern is heightened around flowback and produced water (FPW) generated by the hydraulic fracturing process. FPW is a complex mix of organic and inorganic solutes derived from both the injected hydraulic fracturing fluid and interactions with the subsurface lithology. Few studies to date have systematically investigated the composition of FPW or its individual components. Here, we provide the first systematic characterization of the composition of the solids associated with FPW by analyzing samples from three wells drilled into the Duvernay Formation in Alberta, Canada. The FPW initially returned to the surface with high total dissolved solids (greater than 170 000 mg L-1) and enriched with Fe(ii), silica, sulfate, barium, and strontium. The solids form two distinct phases once the FPW reached the surface: (1) silica-enriched Fe(iii) oxyhydroxides, and (2) a barite-celestine solid solution. We hypothesize that the precipitation of the amorphous silica-enriched Fe(iii) oxyhydroxide is a two-step process, where first the silica precipitates as a function of the cooling of the FPW from elevated subsurface temperatures to ambient surface temperatures. Next, the silica acts as a template for the precipitation of Fe(iii) oxyhydroxide as the diffusion of oxygen into the subsurface causes oxidation of aqueous Fe(ii). The barite-celestine solid solution precipitates solely as a function of cooling. Elevated dissolved Fe concentrations in FPW and modeled saturation indices from five North American shale plays (Marcellus, Fayetteville, Barnett, Bakken, and Denver-Julesburg) indicate that solids similar to those found in Duvernay FPW, specifically Fe(iii) oxyhydroxides, barite and quartz, are likely to occur. With the solids known to carry a significant portion of FPW's toxicity and organic contaminant load, the development of new treatment technologies, such as the oxidation of the Fe(ii) in FPW, may increase FPW reuse and reduce the environmental risk posed by FPW.

Photoferrotrophy, deposition of banded iron formations, and methane production in Archean oceans.

Banded iron formation (BIF) deposition was the likely result of oxidation of ferrous iron in seawater by either oxygenic photosynthesis or iron-dependent anoxygenic photosynthesis-photoferrotrophy. BIF deposition, however, remains enigmatic because the photosynthetic biomass produced during iron oxidation is conspicuously absent from BIFs. We have addressed this enigma through experiments with photosynthetic bacteria and modeling of biogeochemical cycling in the Archean oceans. Our experiments reveal that, in the presence of silica, photoferrotroph cell surfaces repel iron (oxyhydr)oxides. In silica-rich Precambrian seawater, this repulsion would separate biomass from ferric iron and would lead to large-scale deposition of BIFs lean in organic matter. Excess biomass not deposited with BIF would have deposited in coastal sediments, formed organic-rich shales, and fueled microbial methanogenesis. As a result, the deposition of BIFs by photoferrotrophs would have contributed fluxes of methane to the atmosphere and thus helped to stabilize Earth's climate under a dim early Sun.

Determination of the Settling Rate of Clay/Cyanobacterial Floccules.

The mechanisms underpinning the deposition of fine-grained, organic-rich sediments are still largely debated. Specifically, the impact of the interaction of clay particles with reactive, planktonic cyanobacterial cells to the sedimentary record is under studied. This interaction is a potentially major contributor to shale depositional models. Within a lab setting, the flocculation and sedimentation rates of these materials can be examined and measured in a controlled environment. Here, we detail a protocol for measuring the sedimentation rate of cyanobacterial/clay mixtures. This methodology is demonstrated through the description of two sample experiments: the first uses kaolin (a dehydrated form of kaolinite) and Synechococcus sp. PCC 7002 (a marine coccoid cyanobacteria), and the second uses kaolin and Synechocystis sp. PCC 6803 (a freshwater coccoid cyanobacteria). Cyanobacterial cultures are mixed with varying amounts of clay within a specially designed tank apparatus optimized to allow continuous, real-time video and photographic recording. The sampling procedures are detailed as well as a post-collection protocol for precise measurement of chlorophyll a from which the concentration of cyanobacterial cells remaining in suspension can be determined. Through experimental replication, a profile is constructed that displays sedimentation rate.