Andrew R. Zimmerman

Effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil.

When applied to soils, it is unclear whether and how biochar can affect soil nutrients. This has implications both to the availability of nutrients to plants or microbes, as well as to the question of whether biochar soil amendment may enhance or reduce the leaching of nutrients. In this work, a range of laboratory experiments were conducted to determine the effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil. A total of thirteen biochars were tested in laboratory sorption experiments and most of them showed little/no ability to sorb nitrate or phosphate. However, nine biochars could remove ammonium from aqueous solution. Biochars made from Brazilian pepperwood and peanut hull at 600°C (PH600 and BP600, respectively) were used in a column leaching experiment to assess their ability to hold nutrients in a sandy soil. The BP600 biochar effectively reduced the total amount of nitrate, ammonium, and phosphate in the leachates by 34.0%, 34.7%, and 20.6%, respectively, relative to the soil alone. The PH600 biochar also reduced the leaching of nitrate and ammonium by 34% and 14%, respectively, but caused additional phosphate release from the soil columns. These results indicate that the effect of biochar on the leaching of agricultural nutrients in soils is not uniform and varies by biochar and nutrient type. Therefore, the nutrient sorption characteristics of a biochar should be studied prior to its use in a particular soil amendment project.

Removal of heavy metals from aqueous solution by biochars derived from anaerobically digested biomass.

This study examined the ability of two biochars converted from anaerobically digested biomass to sorb heavy metals using a range of laboratory sorption and characterization experiments. Initial evaluation of DAWC (digested dairy waste biochar) and DWSBC (digested whole sugar beet biochar) showed that both biochars were effective in removing a mixture of four heavy metals (Pb(2 +), Cu(2+), Ni(2+), and Cd(2+)) from aqueous solutions. Compared to DAWC, DWSBC demonstrated a better ability to remove Ni and Cd. Further investigations of lead sorption by the two biochars indicated that the removal was mainly through a surface precipitation mechanism, which was confirmed by batch sorption experiments, mathematical modeling, and examinations of lead-laden biochars samples using SEM-EDS, XRD, and FTIR. The lead sorption capacity of the two biochars was close to or higher than 200mmol/kg, which is comparable to that of commercial activated carbons.

Biochar derived from anaerobically digested sugar beet tailings: Characterization and phosphate removal potential

Two biochars were produced from anaerobically digested and undigested sugar beet tailings through slow-pyrolysis at 600°C. The digested sugar beet tailing biochar (DSTC) and raw sugar beet tailing biochar (STC) yields were around 45.5% and 36.3% of initial dry weight, respectively. Compared to STC, DSTC had similar pH and surface functional groups, but higher surface area, and its surface was less negatively charged. SEM-EDS and XRD analyses showed that colloidal and nano-sized periclase (MgO) was presented on the surface of DSTC. Laboratory adsorption experiments were conducted to assess the phosphate removal ability of the two biochars, an activated carbon (AC), and three Fe-modified biochar/AC adsorbents. The DSTC showed the highest phosphate removal ability with a removal rate around 73%. Our results suggest that anaerobically digested sugar beet tailings can be used as feedstock materials to produce high quality biochars, which could be used as adsorbents to reclaim phosphate.

Removal of phosphate from aqueous solution by biochar derived from anaerobically digested sugar beet tailings.

Biochar converted from agricultural residues or other carbon-rich wastes may provide new methods and materials for environmental management, particularly with respect to carbon sequestration and contaminant remediation. In this study, laboratory experiments were conducted to investigate the removal of phosphate from aqueous solution by biochar derived from anaerobically digested sugar beet tailings (DSTC). Batch adsorption kinetic and equilibrium isotherm experiments and post-adsorption characterizations using SEM-EDS, XRD, and FTIR suggested that colloidal and nano-sized MgO (periclase) particles on the biochar surface were the main adsorption sites for aqueous phosphate. Batch adsorption experiments also showed that both initial solution pH and coexisting anions could affect the adsorption of phosphate onto the DSTC biochar. Of the mathematical models used to describe the adsorption kinetics of phosphate removal by the biochar, the Ritchie N_th-order (N=1.14) model showed the best fit. Two heterogeneous isotherm models (Freundlich and Langmuir-Freundlich) fitted the experimental isotherm of phosphate adsorption onto the biochar better than the Langmuir adsorption model. Our results suggest that biochar converted from anaerobically digested sugar beet tailings is a promising alternative adsorbent, which can be used to reclaim phosphate from water or reduce phosphate leaching from fertilized soils. In addition, there is no need to regenerate the exhausted biochar because the phosphate-laden biochar contains abundance of valuable nutrients, which may be used as a slow-release fertilizer to enhance soil fertility and to sequester carbon.

Catechol and humic acid sorption onto a range of laboratory-produced black carbons (biochars).

Although the major influence of black carbon (BC) on soil and sediment organic contaminant sorption is widely accepted, an understanding of the mechanisms and natural variation in pyrogenic carbon interaction with natural organic matter (NOM) is lacking. The sorption of a phenolic NOM monomer (catechol) and humic acids (HA) onto BC was examined using biochars made from oak, pine, and grass at 250, 400, and 650 degrees C. Catechol sorption equilibrium occurred after 14 d and was described by a diffusion kinetic model, while HA required only 1 d and followed pseudo-second-order kinetics. Catechol sorption capacity increased with increasing biochar combustion temperature, from pine < oak < grass and from coarse < fine particle size. At lower catechol concentrations, sorption affinity (Freundlich constant, K(f)) was directly related to micropore surface area (measured via CO(2) sorptometry) indicating the predominance of specific adsorption. In contrast, HA exhibited an order of magnitude less sorption (0.1% versus 1%, by weight) due to its exclusion from micropores. Greater sorption of both catechol and HA occurred on biochars with nanopores, i.e. biochars made at higher temperatures. These findings suggest that addition of BC to soil, via natural fires or biochar amendments, will sequester abundant native OM through sorption.

A geochemical record of eutrophication and anoxia in Chesapeake Bay sediments: anthropogenic influence on organic matter composition

Abstract Organic and inorganic geochemical indicators were examined in a 3-m core collected from the mesohaline region of Chesapeake Bay (CB) to determine how sources of organic matter (OM) have changed during the preceding three centuries of increasing anthropogenic influence in this region. This study also establishes the history of eutrophication and anoxia/hypoxia and relates these processes to changes in OM deposition and preservation and to historical events within the Bays watershed. The sediment record shows that a marked increase in organic carbon (35%–50%), biogenic silica (18%) and total sulfur (42%) occurs between 1934 and 1948. This transition is likely due to increasing anoxic/hypoxic bottom water conditions as indicated by an abrupt change in sulfur speciation. Lipid biomarker distributions indicate that a substantial change in the sources of OM deposited since 1934 has also occurred. Biomarker compounds derived from phytoplankton and microbial sources show a 2- to 4-fold increase in their abundance relative to total organic carbon (TOC) between 1948 and 1975. Using both diagenetic models and information on lipid reactivity, an effort is made to distinguish compositional changes due to changes in OM delivery (both quantity and quality) from changes that may be due to OM degradation. It appears that enhanced OM production in the mesohaline region of CB has contributed to the observed changes in quantity and character of OM preserved in sediments from this site. Increased inorganic fertilizer application and human population growth in the watershed are coincident with the onset of eutrophic and hypoxic conditions in CB, suggesting that anthropogenic activities within estuarine watersheds may exert a substantial influence on carbon cycling processes in estuaries and potentially the coastal ocean.

Effects of chemical, biological, and physical aging as well as soil addition on the sorption of pyrene to activated carbon and biochar.

In this study, the suitability of biochar and activated carbon (AC) for contaminated soil remediation is investigated by determining the sorption of pyrene to both materials in the presence and absence of soil and before as well as after aging. Biochar and AC were aged either alone or mixed with soil via exposure to (a) nutrients and microorganisms (biological), (b) 60 and 110 °C (chemical), and (c) freeze-thaw cycles (physical). Before and after aging, the pH, elemental composition, cation exchange capacity (CEC), microporous SA, and sorption isotherms of pyrene were quantified. Aging at 110 °C altered the physicochemical properties of all materials to the greatest extent (for example, pH increased by up to three units and CEC by up to 50% for biochar). Logarithmic K(Fr) values ranged from 7.80 to 8.21 (ng kg(-1))(ng L(-1))(-nF) for AC and 5.22 to 6.21 (ng kg(-1))(ng L(-1))(-nF) for biochar after the various aging regimes. Grinding biochar to a smaller particle size did not significantly affect the sorption of d(10) pyrene, implying that sorption processes operate on the subparticle scale. Chemical aging decreased the sorption of pyrene to the greatest extent (up to 1.8 log unit for the biochar+soil). The sorption to AC was affected more by the presence of soil than the sorption to biochar was. Our results suggest that AC and biochar have a high sorption capacity for pyrene that is maintained both in the presence of soil and during harsh aging. Both materials could therefore be considered in contaminated land remediation.

Degradation and resilience in Louisiana salt marshes after the BP–Deepwater Horizon oil spill

More than 2 y have passed since the BP–Deepwater Horizon oil spill in the Gulf of Mexico, yet we still have little understanding of its ecological impacts. Examining effects of this oil spill will generate much-needed insight into how shoreline habitats and the valuable ecological services they provide (e.g., shoreline protection) are affected by and recover from large-scale disturbance. Here we report on not only rapid salt-marsh recovery (high resilience) but also permanent marsh area loss after the BP–Deepwater Horizon oil spill. Field observations, experimental manipulations, and wave-propagation modeling reveal that (i) oil coverage was primarily concentrated on the seaward edge of marshes; (ii) there were thresholds of oil coverage that were associated with severity of salt-marsh damage, with heavy oiling leading to plant mortality; (iii) oil-driven plant death on the edges of these marshes more than doubled rates of shoreline erosion, further driving marsh platform loss that is likely to be permanent; and (iv) after 18 mo, marsh grasses have largely recovered into previously oiled, noneroded areas, and the elevated shoreline retreat rates observed at oiled sites have decreased to levels at reference marsh sites. This paper highlights that heavy oil coverage on the shorelines of Louisiana marshes, already experiencing elevated retreat because of intense human activities, induced a geomorphic feedback that amplified this erosion and thereby set limits to the recovery of otherwise resilient vegetation. It thus warns of the enhanced vulnerability of already degraded marshes to heavy oil coverage and provides a clear example of how multiple human-induced stressors can interact to hasten ecosystem decline.

Biochar from anaerobically digested sugarcane bagasse

This study was designed to investigate the effect of anaerobic digestion on biochar produced from sugarcane bagasse. Sugarcane bagasse was anaerobically digested to produce methane. The digested residue and fresh bagasse was pyrolyzed separately into biochar at 600 degrees C in nitrogen environment. The digested bagasse biochar (DBC) and undigested bagasse biochar (BC) were characterized to determine their physicochemical properties. Although biochar was produced from the digested residue (18% by weight) and the raw bagasse (23%) at a similar rate, there were many physiochemical differences between them. Compared to BC, DBC had higher pH, surface area, cation exchange capacity (CEC), anion exchange capacity (AEC), hydrophobicity and more negative surface charge, all properties that are generally desirable for soil amelioration, contaminant remediation or wastewater treatment. Thus, these results suggest that the pyrolysis of anaerobic digestion residues to produce biochar may be an economically and environmentally beneficial use of agricultural wastes.

A review of biochar as a low-cost adsorbent for aqueous heavy metal removal

ABSTRACT As a low-cost adsorbent, biochar can be used as a low-cost adsorbent for wastewater treatment, particularly with respect to treating heavy metals in wastewater. A number of studies have demonstrated effective removal of heavy metals from aqueous solutions by biochar and, in some cases, proven the superiority of biochars to activated carbons. Among several factors affecting the sorption ability of biochars, feedstock materials play a significant role. This review incorporates existing literature to understand the overall sorption behavior of heavy metals on biochar adsorbents. Depending on the biochar type, heavy metal can be removed by different mechanisms such as complexation, physical sorption, precipitation and electrostatic interactions. Mathematical sorption models can be used to understand the efficiency of biochar at removing heavy metals, and promote the application of biochar technology in water treatment.