Importance of site-specific factors for the immobilization of contaminants using biochar and wood-based activated carbon

<p>The use of environmentally friendly low-cost sorbents such as biochar and wood-based activated carbon as soil amendment has shown promising results in immobilizing organic and inorganic contaminants. They can be suitable soil remediation options at sites with residual contamination, where the contaminated hotspot has been removed. The effectiveness of biochar and activated carbon application is site dependent. Specifically, dissolved organic carbon (DOC), pH, and ionic strength in the pore water are important factors which can influence the extent of contaminant immobilization. Although there has been significant progress in developing alternative carbonaceous sorbents, the efficiency of these materials in a diverse range of soil and pore water conditions remains an open question. To address this knowledge gap, the present study investigates the influence of pore water chemistry on sorption of organic and inorganic contaminants to biochar and wood-based activated carbon. Sorption of selected non-polar, polar and ionizable polycyclic aromatic compounds (PACs) and inorganic Cadmium (Cd) to biochar and a wood-based activated carbon was studied under different pore water chemistry conditions. Batch sorption experiments were conducted using an experimental design approach (Box Behnken Design) with three different levels of DOC, pH, and ionic strength, yielding background solutions mimicking a wide spectrum of pore water chemistries. Sorption K<sub>D</sub> values [L/kg] were calculated from aqueous contaminant concentrations after equilibration. Results were analyzed using a response surface methodology (RSM) approach on Minitab 19 and fitted to a model equation using linear, squared and two-way interactions terms.</p><p>Our results show that the ionizable PAC (phenyl phenol) and Cd were most affected by changes in pore water chemistries. For phenyl phenol, the presence of a phenolic group can cause H-bonding and electrostatic attraction and repulsion, while pH-dependent changes in speciation, precipitation and electrostatic attraction can occur for Cd. Sorption of all PACs negatively correlated with DOC, indicating competition of DOC with PACs for sorption sites. Sorption of non-polar (acenaphthene), polar N substituted (carbazole) and ionizable (phenyl phenol) PACs was hindered under acidic conditions, due to precipitation of DOC. For Cd, higher pH and low DOC levels favored sorption. This can be attributed to a lower Cd solubility in the presence of leached phosphate at higher pH, and a predominance of Cd(OH)<sub>2</sub> in the neutral to alkaline regime. Our findings highlight the importance of considering a combination of site- and contaminant-specific factors when planning to apply carbonaceous sorbents for contaminant immobilization, with pH and DOC generally being more important than ionic strength.</p>

Generalized effective stress concept for saturated active clays

Experimental evidence shows that changes in pore water chemistry can significantly affect the mechanical behavior of saturated active clays. Despite this evidence, how the chemical composition of the pore water can be considered in effective stress definition is questionable. This paper develops the concept of generalized effective stress for active clays. To this end, physicochemical studies on water–clay mineral interactions are used to clearly define the different types of ions and water present in an active clay. In particular, the presence of both movable and non-movable ions within the liquid water is highlighted. Taking this into account, thermodynamic and geochemistry principles are applied to the representative elementary volume scale for determining the pore water pressure and redefine the effective stress accordingly. The theoretical development results in the dependence of the effective stress on the pore water chemistry through the effective solute suction variable. Equations for the determination of this chemical variable are developed. The implications of the use of the proposed effective stress concept are investigated using experimental results taken from the literature. The results show advantages both in the interpretation of shear strength and volumetric data, and all support the theoretical explanation underlying the proposed concept.

Pore-water chemistry: A proxy for tracking the signature of ongoing silica diagenesis

ABSTRACT Silica diagenesis leads to dramatic petrophysical variations in the host sediment across the depth of an opal-A to opal-CT transition zone. Predicting the present-day diagenetic status of opal-A to opal-CT transition zones, i.e., active versus fossilized fronts, is essential to constraining the drivers that control abrupt changes in the physical state of sediment. This study assesses whether there are modern signatures of ongoing silica diagenesis in the sediment pore water, and demonstrates the potential for pore-water-chemistry profiles for distinguishing between active opal-CT precipitation and fossil transition zones. Pore-water chemistry, mineralogy, and thermodynamic analyses of the Ocean Drilling Program Wells 794 and 795 indicate that solubility equilibrium has been reached with respect to opal-CT in the transition zones captured by the Neogene biosilica in the Sea of Japan. Even though silica dissolution might be triggering a reverse-weathering process, the equilibrium reached with respect to diagenetic opal strongly suggests that the silica drop across the transition zones is mainly influenced by active opal-A to opal-CT transformation. Owing to abrupt petrophysical variations associated with opal-CT formation, other interstitial profiles—major ions and primary parameters—have been influenced by silica diagenesis. The extremely low silica diffusion fluxes in the sediment, the low permeability of host sediment, and the occurrence of considerable pore-water loss at the depth of the transition zone all support this conclusion that the dissolved species have not been diffused in the sediment at rates comparable to those by pore-water advection. Advection and diffusion, however, appear to have ceased recently because they have failed to smooth the signature of ongoing silica diagenesis. The porosity drop during opal-A to opal-CT diagenesis at Sites 794 and 795 is principally attributed to chemically induced anomalous compaction, causing the sediment framework to lose its strength under fragmentation and extensive opal-A dissolution.