Expanding the Analytical Window for Biochar Speciation: Molecular Comparison of Solvent Extraction and Water-Soluble Fractions of Biochar by FT-ICR Mass Spectrometry.

Biochar, a low-density yet carbon-rich material derived from different organic materials pyrolyzed under low or no oxygen conditions, has been widely studied as a soil amendment, for greenhouse gas mitigation and in remediation of trace element-contaminated soils. Molecular speciation of biochar compounds has been challenging due to low solubility, aggregation, and immense compositional polydispersity that challenges nearly all mass spectrometry methods routinely applied to carbon-based organic materials. Through a combined technique approach that applies advanced analytical strategies, we provide bulk and molecular characterization of Kentucky bluegrass biochar that can be applied to any biomass or biochar sample. First, we characterize Kentucky bluegrass biochar chemical functional groups by solid-state magic-angle spinning dynamic nuclear polarization NMR (MAS-DNP NMR) and resolve aromatic and aliphatic signals from the pyrogenic material and intact plant material. Next, we isolate water-soluble biochar species by solid-phase extraction followed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and identify highly polar, oxygen species across a wide carbon number range. Solvent fractionation of biochar further expands the compositional range and identifies condensed polycyclic aromatic species across nonpolar and polar classes detected by two ionization modes (-ESI and +APPI) by FT-ICR MS. Plotting biochar species with DBE versus carbon number highlights the pericondensed molecular structural motif that persists across numerous heteroatom classes and ionization modes. To the best of our knowledge, this is the first molecular level identification of nonfunctionalized PAHs in biochar extracts by APPI FT-ICR MS. Thus, we identify biochar species that span the same compositional space as coal, heavy oil asphaltenes, and coal tar and correspond to condensed ring PAHs.

Phytostabilization of acidic mine tailings with biochar, biosolids, lime, and locally-effective microbes: Do amendment mixtures influence plant growth, tailing chemistry, and microbial composition?

Abandoned mine lands present persistent environmental challenges to ecosystems and economies; reclamation an important step for overcoming these challenges. Phytostabilization is an elegant and cost-effective reclamation strategy, however, establishing plants on severely degraded soils is problematic, often requiring soil amendment additions. We evaluated whether amendment mixtures composed of lime, biochar, biosolids, and locally effective microbes (LEM) could alleviate the constraints that hinder phytostabilization success. We hypothesized that 1) plants grown in tailings amended with lime, biochar, and biosolids (LBB) would establish faster and grow larger than plants grown in tailings amended with lime only, and 2) the LEM source would influence microbial community function and structure in amended mine tailings. We conducted a greenhouse study that simulated in situ conditions to measure the influence of LBB-LEM amendment blends on plant growth, plant nutrients, metal concentrations, microbial function, and microbial community structure. Blue wildrye [Elymus glaucus Buckley ssp. Jepsonii (Burtt Davy) Gould] was grown in tailings collected from the Formosa mine site amended with various combinations of LBB-LEM. The above and below ground biomass of plants grown in mine tailings amended with LBB was 3 to 4 times larger than the biomass of plants grown in tailings amended only with lime. Although the LEM addition did not influence immediate plant growth, it did affect nutrient content and altered the rhizosphere community membership. As such, it is not yet clear if LEM-driven alterations in microbial membership will advance mine reclamation strategies by improving long-term growth.

Cadmium, copper, lead and zinc accumulation in wild plant species near a lead smelter.

Smelting activities have been shown to increase the likelihood of environmental heavy metal accumulation and bioaccumulation potential within relative proximity to smelter sites. This investigation focused specifically on cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) accumulation in 43 wild plant species and corresponding soils near a Pb smelting contaminated area. Soils in the study area had elevated Cd, Cu, Pb and Zn concentrations, with pollution indices ranked as Cd > Pb > Cu > Zn. Aboveground plant heavy metal concentrations ranked Pb > Zn > Cd > Cu, with plants having greater bioconcentration factor (BCF) values for Cd than for Pb, Cu and Zn. Plant Cd BCF averaged 1.42, while Pb, Cu and Zn averaged 0.128, 0.256 and 0.560, respectively. The greatest Cd BCF value was 5.40 for Dendranthema indicum; Cd accumulation for this species has not been reported previously. The greatest shoot Cd concentration (66.5 mg kg-1) was found in Viola verecunda. Significant correlations existed between plant shoot Cd and Pb concentrations and soil total and DTPA-extractable Cd and Pb. Plant species with greater heavy metal accumulation could potentially be used for phytoextraction in the study area, while those having less accumulation potentially being used to reduce heavy metal flow into the food chain, reducing the health risks associated with elevated heavy metal soil contamination.

Phosphorus Sorption Characteristics in Aluminum-based Water Treatment Residuals Reacted with Dairy Wastewater: 1. Isotherms, XRD, and SEM-EDS Analysis.

We examined P sorption characteristics in Al-based water treatment residuals (Al-WTR) generated from slightly alkaline surface water and in an organic residual composite (WW-Al/O-WTR), produced by using the Al-WTR to treat organic-rich and high P concentration dairy wastewater. Solids from both residuals were examined using scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD), and exposed to P additions of 0 to 4000 mg L in a sorption experiment. The Al-WTR removed ∼97% of the added P, whereas WW-Al/O-WTR removed only 78% of the added P in the addition range of 0 to 100 mg P L. With P additions of ≥100 mg L, the removal rate declined to <38% by Al-WTR and to 16% by WW-Al/O-WTR, possibly implying a change in sorption mechanisms. Analysis by XRD indicated that the major mineral was calcite, with some silica and poorly crystalline Al hydroxides. Analysis by SEM-EDS, which used three-element overlay maps of the residual surfaces, indicated that P was sparsely sorbed on both calcic and Al (hydr)oxide surfaces, along with a few clusters, even at low P concentrations of the treated waters. Ternary clusters of P, Al, and Ca were more abundant on the WW-Al/O-WTR. Carbon distribution suggested that organic substances covered Al surfaces. Sorption of P onto WW-Al/O-WTR may be reversible due to relatively weak Ca-P and Al-P bonds induced by the slight alkaline nature and in the presence of organic moieties, enhancing the WW-Al/O-WTR potential to act as a P source, rather than a P sink, in agricultural applications.

Phosphorus Sorption to Aluminum-based Water Treatment Residuals Reacted with Dairy Wastewater: 2. X-Ray Absorption Spectroscopy.

Phosphorus capture from wastewater can decrease water pollution and provide a P-rich fertilizer alternative for use in agricultural production. This study was conducted to elucidate P retention mechanisms in Al-based water treatment residuals (Al-WTR) to gain insight regarding P sorption and the potential for P release from Al-WTR after reaction with dairy wastewater. Synchrotron-based microfocused X-ray fluorescence (micro-XRF) spectrometry, bulk P -edge X-ray absorption near edge structure spectroscopy (XANES), and P -edge micro-XANES spectroscopy were used to determine P distribution and speciation within the Al-WTR materials. Bulk XANES analyses indicated a shift from ∼56 P atom % Ca-associated P in the initial Al-WTR to ∼32% P atom % Ca-associated P after reaction with wastewater; Al-associated P made up the remainder of the P species. According to XANES analyses, adsorption appeared to be the primary P retention mechanism in the Al-WTR materials. However, micro-XANES analyses depicted a more complicated picture of P retention mechanisms, with regions of primarily Al-associated P, regions of primarily Ca-associated P, regions of mixed Al- and Ca-associated P, and distinct apatite- or octocalcium phosphate-like P grains. Synchrotron micro-XRF mapping further suggested that exposure of the aggregate exteriors to wastewater caused P to diffuse into the porous Al-WTR aggregates. Organic P species were not explicitly identified via P -edge XANES despite high organic matter content, suggesting that organic P may have been predominantly associated with mineral surfaces. Although diffusion and sorption to Al may decrease P bioavailability, Ca-associated P may increase P bioavailability from Al-WTR that is reused as a soil amendment.

Path Analyses of Grain P, Zn, Cu, Fe, and Ni in a Biosolids-Amended Dryland Wheat Agroecosystem.

Land application of biosolids is an effective means of recycling plant nutrients and is the primary method of biosolids reuse endorsed by the USEPA. One issue concerning biosolids application is the extent of the contribution of biosolids-borne plant nutrients to the overall crop concentration and uptake or removal of these nutrients. We studied the effects of biosolids application on wheat ( L.) grain P, Zn, Cu, Fe, and Ni concentrations and uptake (removal) at two dryland agroecosystem sites from 1993 to 2014. We hypothesized that biosolids would have the greatest impact on wheat grain and uptake compared with ammonium bicarbonate-diethylenetriaminepentaacetic acid (AB-DTPA)-extractable nutrient levels, soil pH, or soil organic C concentrations. We used path analyses in combination with multiple linear regression to differentiate the direct, indirect, and total effects of cumulative biosolids applications, soil AB-DTPA, soil pH, and organic C. Biosolids rates, applied biennially from 1993 to 2014 at the beginning of a wheat-fallow rotation, were 0, 2.24, 4.48, 6.72, 8.96, and 11.2 Mg ha. None of the parameters had significant direct, indirect, or total effects on grain concentrations. Biosolids applications had the greatest positive direct impact compared with AB-DTPA levels, soil pH, or soil organic C on P, Zn, Fe, and Ni uptake (removal), whereas AB-DTPA had the greatest positive direct impact on Cu uptake. Soil AB-DTPA, pH, and organic C directly affected some grain concentrations and cumulative uptake, but no consistent trends were noted. This pathway approach allowed differentiation between causation and simple correlation for the effects of cumulative biosolids applications on wheat P, Zn, Cu, Fe, and Ni cumulative uptake but did not provide these same results for grain concentrations.

Uptake coefficients for biosolids-amended dryland winter wheat.

The USEPA adapted a risk assessment approach in biosolids regulations that includes the use of an uptake coefficient (UC) (i.e., the ratio of plant concentration to quantity of element added) to determine limitations on selected elemental additions. The nature of the risk assessment requires UCs to be constants. Our hypothesis was that the UC for Cu, Fe, Mo, Ni, P, and Zn for biosolids-amended dryland winter wheat ( L.) decreases with multiple biosolids applications at the same location. We applied up to 10 applications to two sites (designated North Bennett A and B) in eastern Colorado at rates from 2.24 to 11.2 Mg ha per application from 1993 to 2013. Results indicated that grain concentrations for all six elements followed no discernible trend as the number of biosolids applications increased. The UC values for these elements compared with the number of biosolids applications followed exponential decay models ( ranged from 0.329 to 0.879). Consequently, UC values will likely not provide constants for risk assessment where multiple biosolids applications are made on the same site. We found that the slope between cumulative elemental removal by grain (kg ha) to the cumulative amount of element added with biosolids (kg ha) provides a constant over the number of biosolids additions ( ranged from 0.471 to 0.990). As compared with the USEPA approach, our strategy of looking at cumulative changes may provide better estimations of wheat-grain concentrations for risk assessment of biosolids-borne elements.

Phosphorus losses from an irrigated watershed in the northwestern United States: case study of the upper snake rock watershed.

Watersheds using surface water for irrigation often return a portion of the water to a water body. This irrigation return flow often includes sediment and nutrients that reduce the quality of the receiving water body. Research in the 82,000-ha Upper Snake Rock (USR) watershed from 2005 to 2008 showed that, on average, water diverted from the Snake River annually supplied 547 kg ha of total suspended solids (TSS), 1.1 kg ha of total P (TP), and 0.50 kg ha of dissolved P (DP) to the irrigation tract. Irrigation return flow from the USR watershed contributed 414 kg ha of TSS, 0.71 kg ha of TP, and 0.32 kg ha of DP back to the Snake River. Significantly more TP flowed into the watershed than returned to the Snake River, whereas there was no significant difference between inflow and return flow loads for TSS and DP. Average TSS and TP concentrations in return flow were 71 and 0.12 mg L, respectively, which exceeded the TMDL limits of 52 mg L TSS and 0.075 mg L TP set for this section of the Snake River. Monitoring inflow and outflow for five water quality ponds constructed to reduce sediment and P losses from the watershed showed that TSS concentrations were reduced 36 to 75%, but DP concentrations were reduced only 7 to 16%. This research showed that continued implementation of conservation practices should result in irrigation return flow from the USR watershed meeting the total maximum daily load limits for the Snake River.

Harnessing Phosphorous (P) Fertilizer-Insensitive Bacteria to Enhance Rhizosphere P Bioavailability in Legumes.

Phosphorous (P) is widely used in agriculture; yet, P fertilizers are a nonrenewable resource. Thus, mechanisms to improve soil P bioavailability need to be found. Legumes are efficient in P acquisition and, therefore, could be used to develop new technologies to improve soil P bioavailability. Here, we studied different species and varieties of legumes and their rhizosphere microbiome responses to low-P stress. Some varieties of common beans, cowpeas, and peas displayed a similar biomass with and without P fertilization. The rhizosphere microbiome of those varieties grown without P was composed of unique microbes displaying different levels of P solubilization and mineralization. When those varieties were amended with P, some of the microbes involved in P solubilization and mineralization decreased in abundance, but other microbes were insensitive to P fertilization. The microbes that decreased in abundance upon P fertilization belonged to groups that are commonly used as biofertilizers such as Pseudomonas and Azospirillum. The microbes that were not affected by P fertilization constitute unique species involved in P mineralization such as Arenimonas daejeonensis, Hyphomicrobium hollandicum, Paenibacillus oenotherae, and Microlunatus speluncae. These P-insensitive microbes could be used to optimize P utilization and drive future sustainable agricultural practices to reduce human dependency on a nonrenewable resource.

Tomato domestication rather than subsequent breeding events reduces microbial associations related to phosphorus recovery.

Legacy phosphorus (P) is a reservoir of sparingly available P, and its recovery could enhance sustainable use of nonrenewable mineral fertilizers. Domestication has affected P acquisition, but it is unknown if subsequent breeding efforts, like the Green Revolution (GR), had a similar effect. We examined how domestication and breeding events altered P acquisition by growing wild, traditional (pre-GR), and modern (post-GR) tomato in soil with legacy P but low bioavailable P. Wild tomatoes, particularly accession LA0716 (Solanum pennellii), heavily cultured rhizosphere P solubilizers, suggesting reliance on microbial associations to acquire P. Wild tomato also had a greater abundance of other putatively beneficial bacteria, including those that produce chelating agents and antibiotic compounds. Although wild tomatoes had a high abundance of these P solubilizers, they had lower relative biomass and greater P stress factor than traditional or modern tomato. Compared to wild tomato, domesticated tomato was more tolerant to P deficiency, and both cultivated groups had a similar rhizosphere bacterial community composition. Ultimately, this study suggests that while domestication changed tomato P recovery by reducing microbial associations, subsequent breeding processes have not further impacted microbial P acquisition mechanisms. Selecting microbial P-related traits that diminished with domestication may therefore increase legacy P solubilization.

Use of standardized procedures to evaluate metal leaching from waste foundry sands.

As part of the casting process, foundries create sand molds and cores to hold the molten metal to specific dimensional tolerances. Although most of the waste foundry sands (WFSs) from this process are land filled, there is great interest in diverting them for use in agricultural and geotechnical applications. One potential limitation to their beneficial use is concern that the WFSs will leach high levels of trace metals. The aim of this study was to quantify Ag, Ba, Cd, Cr, Cu, Ni, Pb, and Zn in leaching extracts from 96 waste molding and core sands from ferrous and nonferrous foundries. The procedures used to assess leaching in the WFSs were the Extraction Procedure, the Toxicity Characteristic Leaching Procedure, and the American Society for Testing and Materials water extraction procedure. The metal extract concentrations were compared with those found in virgin silica sands and Argentinean and U.S. hazardous waste laws to determine if the WFSs met toxicity limits. Regardless of metal cast and sand binder type, the majority of the WFS extracts analyzed contained metal concentrations similar to those found in virgin sand extracts and were below levels considered hazardous. However, 4 of 28 sands that used alkyd urethane binder were deemed hazardous because Pb concentrations in these sands were found to exceed regulatory thresholds. Although other regulated metals, such as As, Hg, and Se, were not analyzed in the extracts, this dataset provides additional evidence that many WFSs have a low metal leaching potential.

Fermentation affects heavy metal bioaccessibility in Chinese mantou.

Effect of different fermentation methods on heavy metal bioaccessibilities in wheat flour is undetermined. In this work, gastric and gastrointestinal heavy metal bioaccessibility in wheat flour products (control-wheat dough, T1-mantou made with normally fermented dough, T2-mantou made with over-fermented dough and T3-mantou made with over-fermented dough + Na2CO3) made from two wheat flour samples (NX and QD) was assessed via a modified physiologically-based extraction test. Cadmium, Zn and Mn bioaccessibility in the gastric phase (GP) was greater than in the gastrointestinal phase (GIP), yet the opposite was observed for Cu (p < 0.05). Lead bioaccessibility in the GIP of the QD sample was 1.37-4.08 times greater than that in the GP, while only the control had greater bioaccessibility in the GIP than that in the GP (p < 0.05) for the NX sample. Treatments T2 and T3 had greater Cd, Cu, Zn and Mn bioaccessibilities than the control and T1 in the GP (p < 0.05). In the GIP, however, only T3 had greater Mn bioaccessibility than the control for the NX sample. Enhanced degradation of the heavy metal-phytate following over-fermentation may have led to greater heavy metal bioaccessibility. Results should help food processors reduce human absorption of excessive heavy metals present in wheat flour foods.

Heavy metal distribution in wheat plant components following foliar Cd application.

Atmospheric deposition of Cd, from anthropogenic activities, can be directly deposited onto and absorbed into wheat plants, yet, how foliar absorbed Cd is translocated in wheat plants is not well understood. A pot experiment investigated foliar Cd application on the accumulation and distribution of heavy metals in various wheat parts. Wheat was grown in a Cd/heavy metal contaminated soil, and from grain heading to the filling stage, 0, 10, 20, 30 and 40 mg kg-1 Cd solution was sprayed repeatedly on leaves (grain heads were covered). Foliar Cd application had no effect on grain yield and Cd concentration (3.01-3.51 mg kg-1 for all treatments), while increased flag leaf blade and sheath Cd concentrations by 1.06-2.77 and 0.00-0.66 times, respectively. Cadmium concentration in the center of the peduncle, from the 40 mg kg-1 Cd solution treatment, was 1.41 times that of the control (10.3 vs 7.30 mg kg-1). Foliar Cd application also increased Cd accumulation (concentration × mass) of the flag leaf blade and sheath. Rachis and grain Pb concentrations were reduced, while stem Pb concentration was increased by Cd application. Cadmium application negatively affected whole plant Ni accumulation and concentration of certain wheat parts; Ni absorption inhibition may have occurred in roots via the downward transport of Cd. Overall results implied that the predominant portion of foliar applied Cd was retained in leaves, while lesser portions migrated to peduncle or root and affected the absorption/distribution of other metals in wheat plants. These results are important for further discerning the mechanism of wheat grain Cd accumulation, especially when grain is raised in areas where atmospheric deposition of Cd (e.g., near smelting facilities) is an issue from an environmental and human health perspective.

Effect of soluble phosphate and bentonite amendments on lead and cadmium bioavailability and bioaccessibility in a contaminated soil.

Effect of commonly used heavy metal immobilizing agents on risks of soil heavy metals has not been well investigated. In this work, a contaminated acidic soil (total Cd = 8.05, total Pb = 261 mg kg-1) was amended with soluble phosphate (P: 160 mg kg-1) and bentonite (3 g kg-1) and incubated for 360 d. The soil was then added to mouse feed at 1:9 soil: feed ratio (weight) and fed to mouse for 10 days, after which the liver, kidney and bone Pb and Cd concentrations were measured. The amended soils were extracted with SBRC and PBET to assay bioaccessibility, and extracted with DTPA to assess the environmental availability. The amendments did not affect the DTPA-Pb/Cd significantly (p > 0.05), while the Cd bioaccessibility in the gastric phase of the SBRC assay was reduced from 90.0 to 20.4 % for the bentonite amended treatment (p < 0.05). Kidney Pb and Cd concentrations of the mice fed with feed containing phosphate spiked soil was 80.2 and 66.0 % lower than the control mice fed with unamended soil (CK), respectively. Significant linear correlations were found between DTPA-extractable concentration and kidney concentrations for Pb/Cd. The effect of amendment on Pb/Cd bioavailability differed between the results calculated with different endpoints. The phosphate amendment resulted in 82.7 and 34.3 % lower Pb RBA compared with the unamended soil calculated with kidney and kidney+liver+bone Pb concentrations, respectively, and 68.8 and 49.7 % lower Cd RBA than the control with kidney and kidney+liver concentrations, respectively. However, no significant effect was observed with both amendments when the RBA was calculated with liver or bone Pb/Cd concentrations, or on Pb RBA with kidney, liver or bone metal concentrations. Results indicate the complex effect of amendments on organ, tissue and overall health risk of soil Pb/Cd to animal/human.

Cadmium and lead bioavailability to poultry fed with contaminated soil-spiked feed.

Geophagy is common for free-range chickens, however, the relative bioavailability (RBA) of heavy metals in contaminated soils consumed by chickens has not fully investigated. In this work, chickens were fed diets increasingly spiked with a contaminated soil (Cd = 105, Pb = 4840 mg kg-1; 3, 5, 10, 20 and 30 % of overall feed by weight), or Cd/Pb reagent spikes (from CdCl2 or Pb(Ac)2), for 23 d. After the study period, chicken liver, kidney, femur and gizzard samples were analyzed for Cd and Pb concentrations, and organ/tissue metal concentrations were used to calculate Cd and Pb RBA. Linear dose response curves (DRCs) were established for both Cd/Pb reagents-spiked and soil-spiked treatments. Femur Cd concentrations of soil-spiked treatments were two times of Cd-spiked treatments with similar feed Cd levels, while feed spiked with Cd or Pb also resulted in elevated Pb or Cd concentrations in some organ/tissues. Metal RBA was calculated using three different methods. Most Cd and Pb RBA values were in the range 50-70 %, with the chicken gizzard as a potential endpoint for bioaccessible Cd and Pb. Cadmium and Pb bioavailability values can help with more precise estimation of Cd and Pb accumulation in chicken following heavy metal-contaminated soil ingestion, with overall results helping to protect human health.

Electron donation of Fe-Mn biochar for chromium(VI) immobilization: Key roles of embedded zero-valent iron clusters within iron-manganese oxide.

The dense surface passivation layer on zero-valent iron (ZVI) restricts its efficiency for water decontamination, causing a poor economy and waste of resources. Herein, we found that the ZVI on Fe-Mn biochar could afford a high electron-donating efficiency for the Cr(VI) reduction and immobilization. Over 78.0% of Fe in the Fe-Mn biochar was used for the Cr(VI) reduction and immobilization, i.e., 56.2 - 161.7 times higher than the commercial ZVI (0.5%) and modified ZVI (0.9 -1.3%), indicating that the unique ZVI species in Fe-Mn biochar offered an outstanding Fe utilization efficiency. We proposed that oxygen atoms in the FeO in the FeMnO2 precursor were removed during pyrolysis with biochar while the MnO skeleton was preserved, forming the embedded ZVI clusters within Fe-Mn oxide. The unique structure inhibited the formation of the Fe-Cr complex on Fe(0), which would facilitate the electron transfer between core Fe(0) and Cr(VI). Moreover, the surface FeMnO2 inhibited the diffusion of Fe and facilitated its affinity with pollutants, thus supporting higher efficiency for pollutant immobilization. The preserved performance of Fe-Mn biochar was proved in industrial wastewater and after long-term oxidation process, and the economic benefit was evaluated. This work provides a new approach for developing active ZVI-based materials with high Fe utilization efficiency and economics for water pollution control.

Magnesium activation affects the properties and phosphate sorption capacity of poultry litter biochar.

Biochars with a high affinity for phosphorus (P) are promising soil amendments for reducing P in agricultural run-off. Poultry litter (PL) is an abundant biochar feedstock. However, PL-derived biochars are typically high in soluble P and therefore require chemical modification to become effective P sorbents. This study investigated the effect of magnesium (Mg) activation on extractable P (EP) and P sorption capacities of PL-derived biochars. Biochar was produced at 500-900 °C from PL activated with 0-1 M Mg. Three differentially aged PL feedstocks were evaluated (1-, 3-5-, and 7-9-year-old). Increased Mg activation level and pyrolysis temperature both resulted in EP reductions from the biochars. Specifically, biochars produced at temperatures ≥ 700 °C from PL activated with ≥ 0.25 M Mg had negligible EP. X-ray diffractograms indicated that increased Mg loading favored the formation of stable Mg3(PO4)2 phases while increasing temperature favored the formation of both Mg3(PO4)2 and Ca5(PO4)3OH. Maximum P sorption capacities (Pmax) of the biochars were estimated by fitting Langmuir isotherms to batch sorption data and ranged from 0.66-10.35 mg g-1. Average Pmax values were not affected by PL age or pyrolysis temperature; however, biochars produced from 1 M Mg-activated PL did have significantly higher average Pmax values (p < 0.05), likely due to a greater abundance of MgO. Overall, the results demonstrated that Mg activation is an effective strategy for producing PL-derived biochars with the potential ability to reduce P loading into environmentally sensitive ecosystems.

Environmental benefits of biochar.

Understanding and improving environmental quality by reducing soil nutrient leaching losses, reducing bioavailability of environmental contaminants, sequestering C, reducing greenhouse gas emissions, and enhancing crop productivity in highly weathered or degraded soils, has been the goal of agroecosystem researchers and producers for years. Biochar, produced by pyrolysis of biomass, may help attain these goals. The desire to advance understanding of the environmental and agronomic implication of biochar utilization led to the organization of the 2010 American Society of Agronomy-Soil Science Society of America Environmental Quality Division session titled "Biochar Effects on the Environment and Agricultural Productivity." This specialized session and sessions from other biochar conferences, such as the 2010 U.S. Biochar Initiative and the Biochar Symposium 2010 are the sources for this special manuscript collection. Individual contributions address improvement of the biochar knowledge base, current information gaps, and future biochar research needs. The prospect of biochar utilization is promising, as biochars may be customized for specific environmental applications.

Biochar: a synthesis of its agronomic impact beyond carbon sequestration.

Biochar has been heralded as an amendment to revitalize degraded soils, improve soil carbon sequestration, increase agronomic productivity, and enter into future carbon trading markets. However, scientific and economic technicalties may limit the ability of biochar to consistently deliver on these expectations. Past research has demonstrated that biochar is part of the black carbon continuum with variable properties due to the net result of production (e.g., feedstock and pyrolysis conditions) and postproduction factors (storage or activation). Therefore, biochar is not a single entity but rather spans a wide range of black carbon forms. Biochar is black carbon, but not all black carbon is biochar. Agronomic benefits arising from biochar additions to degraded soils have been emphasized, but negligible and negative agronomic effects have also been reported. Fifty percent of the reviewed studies reported yield increases after black carbon or biochar additions, with the remainder of the studies reporting alarming decreases to no significant differences. Hardwood biochar (black carbon) produced by traditional methods (kilns or soil pits) possessed the most consistent yield increases when added to soils. The universality of this conclusion requires further evaluation due to the highly skewed feedstock preferences within existing studies. With global population expanding while the amount of arable land remains limited, restoring soil quality to nonproductive soils could be key to meeting future global food production, food security, and energy supplies; biochar may play a role in this endeavor. Biochar economics are often marginally viable and are tightly tied to the assumed duration of agronomic benefits. Further research is needed to determine the conditions under which biochar can provide economic and agronomic benefits and to elucidate the fundamental mechanisms responsible for these benefits.

Analysis of total metals in waste molding and core sands from ferrous and non-ferrous foundries.

Waste molding and core sands from the foundry industry are successfully being used around the world in geotechnical and soil-related applications. Although waste foundry sands (WFSs) are generally not hazardous in nature, relevant data is currently not available in Argentina. This study aimed to quantify metals in waste molding and core sands from foundries using a variety of metal-binder combinations. Metal concentrations in WFSs were compared to those in virgin silica sands (VSSs), surface soils and soil guidance levels. A total analysis for Ag, Al, Ba, Be, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, Te, Tl, V, and Zn was conducted on 96 WFSs and 14 VSSs collected from 17 small and medium-sized foundries. The majority of WFSs analyzed, regardless of metal cast and binder type, contained metal concentrations similar to those found in VSSs and native soils. In several cases where alkyd urethane binder was used, Co and Pb concentrations were elevated in the waste sands. Elevated Cr, Mo, Ni, and Tl concentrations associated with VSSs should not be an issue since these metals are bound within the silica sand matrix. Because of the naturally low metal concentrations found in most WFSs examined in this study, they should not be considered hazardous waste, thus making them available for encapsulated and unencapsulated beneficial use applications.