Pyrolysis-induced phosphorus transformations for biosolids from diverse sources.

Biosolids have been long used as a soil amendment to promote nutrient recovery. The readily releasable forms of nutrients present in this biowaste, such as phosphorus (P), along with their over application, can be detrimental to the environment, causing eutrophication. Pyrolysis, the thermal decomposition of organic materials at elevated temperature and low oxygen, seems to be a promising strategy to lower P release from biowastes such as biosolids. We pyrolyzed biosolids from various treatments and locations (Florida and Illinois; Galicia, Spain; and São Paulo, Brazil) to convert to biochar. Our objectives were (a) to use solid-state assessments, such as X-ray diffraction and scanning electron microscopy, and chemical assessments, such as water-soluble P (WSP), pH, Mehlich 3-extractable P (M3-P), total P (TP), and total Kjeldahl nitrogen, to evaluate changes caused by the conversion and (b) to compare P leaching potentials of biosolids and their corresponding biochars on two soils with varying P retention capacities. Pairwise comparisons indicated that biochar conversion significantly increased TP in the final material, but the absolute WSP decreased. However, M3-P remained the same after conversion to biochar. Cumulative P leached as a fraction of TP was greater for biosolids than their corresponding biochars. Two soils with contrasting P retention capacities predictably differed in P leaching behaviors as amended with biosolids and biochars. Differences suggest that future research could evaluate the efficacy of using mixtures of biosolids and biochar for a given soil to maintain soil fertility while reducing environmental P loss risk.

Report of IRPA task group on issues and actions taken in response to the change in eye lens dose limit.

In 2018, the International Radiation Protection Association (IRPA) established its third task group (TG) on the implementation of the eye lens dose limit. To contribute to sharing experience and raising awareness within the radiation protection community about protection of workers in exposure of the lens of the eye, the TG conducted a questionnaire survey and analysed the responses. This paper provides an overview of the results of the questionnaire.

Valorization of farm pond biomass as fertilizer for reducing basin-scale phosphorus losses.

Long-term fertilizer phosphorus (P) inputs are causing phosphorous saturation of agricultural soils globally. The saturation is spreading to the edge-of-the-farm stormwater detention systems (SDSs) from where the legacy P is potentially being released to downstream surface waters. We use site-specific and literature data for P-saturated SDSs, to develop and evaluate the biogeochemical and economic feasibility of a P recycling program that targets both low (LIC, sugarcane) and high intensity cropping (HIC, fresh-produce) systems within a watershed. The focus is to close the P cycle loop to rejuvenate P sink function of SDSs. It involves harvesting and composting the SDS's biomass and it's on-farm use as an organic fertilizer for crops. Results showed that harvesting-composting can conservatively increase the P retention from 50% to 77% for HIC and almost complete treatment for LIC. Beyond potentially increasing yield and improving soil health, compost use can further increase in-field retention of P (and water). Additional costs incurred in harvesting and composting can be offset by the economic value of compost and the reduction in State's expenditure on regional P treatment systems. Treatment costs were $26/kg of P for HIC and $42/kg for LIC, 10 times less than the current state expenditure of $355-$909/kg P using constructed wetlands. We propose an incentivized, payment for services (PS) program, where producers are paid for P recycling. The PS program considers the intensity of cropping systems and their location along the drainage network from headwaters to the outlet, to achieve basin-scale P load reduction. The LIC SDSs recover regional P by passing the public water through them while recycling is implemented at the HIC. The estimated basin-scale P retention with harvest-compost approach was 854 metric tons, 5 times the P that entered the Everglades Protection Area in 2018, at 88%-93% less cost than the State treatment systems.

Arsenic release from Floridan Aquifer rock during incubations simulating aquifer storage and recovery operations.

While aquifer storage and recovery (ASR) is becoming widely accepted as a way to address water supply shortages, there are concerns that it may lead to release of harmful trace elements such as arsenic (As). Thus, mechanisms of As release from limestone during ASR operations were investigated using 110-day laboratory incubations of core material collected from the Floridan Aquifer, with treatment additions of labile or refractory dissolved organic matter (DOM) or microbes. During the first experimental phase, core materials were equilibrated with native groundwater lacking in DO to simulate initial non-perturbed anaerobic aquifer conditions. Then, ASR was simulated by replacing the native groundwater in the incubations vessels with DO-rich ASR source water, with DOM or microbes added to some treatments. Finally, the vessels were opened to the atmosphere to mimic oxidizing conditions during later stages of ASR. Arsenic was released from aquifer materials, mainly during transitional periods at the beginning of each incubation stage. Most As released was during the initial anaerobic experimental phase via reductive dissolution of Fe oxides in the core materials, some or all of which may have formed during the core storage or sample preparation period. Oxidation of As-bearing Fe sulfides released smaller amounts of As during the start of later aerobic experimental phases. Additions of labile DOM fueled microbially-mediated reactions that mobilized As, while the addition of refractory DOM did not, probably due to mineral sorption of DOM that made it unavailable for microbial utilization or metal chelation. The results suggest that oscillations of groundwater redox conditions, such as might be expected to occur during an ASR operation, are the underlying cause of enhanced As release in these systems. Further, ASR operations using DOM-rich surface waters may not necessarily lead to additional As releases.

Physicochemical and sorptive properties of biochars derived from woody and herbaceous biomass.

It is unclear how the properties of biochar control its ability to sorb metals. In this work, physicochemical properties of a variety of biochars, made from four types of feedstock at three pyrolysis temperatures (300, 450 and 600°C) were compared to their ability to sorb arsenic (As) and lead (Pb) in aqueous solutions. Experimental results showed that both feedstock types and pyrolysis temperature affected biochar's production rate, i.e., ratio of mass of biochar and biomass, thermal stability, elemental composition, non-combustible component (NCC) content, pH values, surface areas and thus their sorption ability to the two metals in aqueous solution. In general, the high temperature biochars had low O/C and H/C ratios, were more carbonized with larger surface area, and were more concentrated with alkaline cations. In addition, biochars made from woody feedstocks had larger surface area, but lower NCC contents than that made from grasses under the same conditions. Although all the tested biochars removed both As and Pb from aqueous solutions, they showed different sorption abilities because of the variations in properties. Statistical analyses suggested that feedstock type affected the sorption ability of the biochars to both As and Pb significantly (p<0.001). Pyrolysis temperature, however, showed little influence on biochar sorption of Pb in aqueous solutions. Statistical analyses also showed that electrostatic interaction played an important role in controlling the sorption of both As(V) and Pb(II) onto the biochar. Other mechanisms, such as precipitation and surface complexation, could also control the sorption of Pb(II) onto the biochars.

Manganese oxide-modified biochars: preparation, characterization, and sorption of arsenate and lead.

This work explored two modification methods to improve biochar's ability to sorb arsenic (As) and lead (Pb). In one, pine wood feedstock was pyrolyzed in the presence of MnCl2·4H2O (MPB) and in the other it was impregnated with birnessite via precipitation following pyrolysis (BPB). The resulting biochars were characterized using thermogravimetry, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analyses. The dominant crystalline forms of Mn oxides in the MPB and BPB were manganosite and birnessite, respectively. Batch sorption studies were carried out to determine the kinetics and magnitude of As(V) and Pb(II) onto the biochars. As(V) and Pb(II) sorption capacities of MPB (0.59 and 4.91 g/kg) and BPB (0.91 and 47.05 g/kg) were significantly higher than that of the unmodified biochar (0.20 and 2.35 g/kg). BPB showed the highest sorption enhancement because of the strong As(V) and Pb(II) affinity of its birnessite particles.

Removal of arsenic by magnetic biochar prepared from pinewood and natural hematite.

There is a need for the development of low-cost adsorbents to removal arsenic (As) from aqueous solutions. In this work, a magnetic biochar was synthesized by pyrolyzing a mixture of naturally-occurring hematite mineral and pinewood biomass. The resulting biochar composite was characterized with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDS). In comparison to the unmodified biochar, the hematite modified biochar not only had stronger magnetic property but also showed much greater ability to remove As from aqueous solution, likely because the γ-Fe2O3 particles on the carbon surface served as sorption sites through electrostatic interactions. Because the magnetized biochar can be easily isolated and removed with external magnets, it can be used in various As contaminant removal applications.

Interaction effects of climate and land use/land cover change on soil organic carbon sequestration.

Historically, Florida soils stored the largest amount of soil organic carbon (SOC) among the conterminous U.S. states (2.26 Pg). This region experienced rapid land use/land cover (LULC) shifts and climate change in the past decades. The effects of these changes on SOC sequestration are unknown. The objectives of this study were to 1) investigate the change in SOC stocks in Florida to determine if soils have acted as a net sink or net source for carbon (C) over the past four decades and 2) identify the concomitant effects of LULC, LULC change, and climate on the SOC change. A total of 1080 sites were sampled in the topsoil (0-20 cm) between 2008 and 2009 representing the current SOC stocks, 194 of which were selected to collocate with historical sites (n = 1251) from the Florida Soil Characterization Database (1965-1996) for direct comparison. Results show that SOC stocks significantly differed among LULC classes--sugarcane and wetland contained the highest SOC, followed by improved pasture, urban, mesic upland forest, rangeland, and pineland while crop, citrus and xeric upland forest remained the lowest. The surface 20 cm soils acted as a net sink for C with the median SOC significantly increasing from 2.69 to 3.40 kg m(-2) over the past decades. The SOC sequestration rate was LULC dependent and controlled by climate factors interacting with LULC. Higher temperature tended to accelerate SOC accumulation, while higher precipitation reduced the SOC sequestration rate. Land use/land cover change observed over the past four decades also favored the C sequestration in soils due to the increase in the C-rich wetland area by ~140% and decrease in the C-poor agricultural area by ~20%. Soils are likely to provide a substantial soil C sink considering the climate and LULC projections for this region.

Enhanced Cr(VI) reduction and As(III) oxidation in ice phase: important role of dissolved organic matter from biochar.

This study evaluated the impact of DOM from two biochars (sugar beet tailing and Brazilian pepper) on Cr(VI) reduction and As(III) oxidation in both ice and aqueous phases with a soil DOM as control. Increasing DOM concentration from 3 to 300mgCL(-1) enhanced Cr(VI) reduction from 20% to 100% and As(III) oxidation from 6.2% to 25%; however, Cr(VI) reduction decreased from 80-86% to negligible while As(III) oxidation increased from negligible to 18-19% with increasing pH from 2 to 10. Electron spin resonance study suggested semiquinone radicals in DOM were involved in As(III) oxidation while Fourier transform infrared analysis suggested that carboxylic groups in DOM participated in both Cr(VI) reduction and As(III) oxidation. During Cr(VI) reduction, part of DOM (∼10%) was oxidized to CO2. The enhanced conversion of Cr(VI) and As(III) in the ice phase was due to the freeze concentration effect with elevated concentrations of electron donors and electron acceptors in the grain boundary. Though DOM enhanced both Cr(VI) reduction and As(III)oxidation, Cr(VI) reduction coupled with As(III) oxidation occurred in absence of DOM. The role of DOM, Cr(VI) and/or As(III) in Cr and As transformation may provide new insights into their speciation and toxicity in cold regions.

Ionic strength reduction and flow interruption enhanced colloid-facilitated Hg transport in contaminated soils.

The effects of ionic strength (IS) reduction (5-0.05mM) and flow interruption (FI, flow stopped for 7d) on colloid and Hg release in the leachate were examined in column experiment. Two Hg contaminated soils (13.9 and 146mg/kg) were used, with Hg concentrations in colloids being 2-4 times greater than bulk soils. Based on sequential extraction, Hg concentrations in organic matter (OM) fraction were the most abundant in soils (31-48%). Column leaching after IS reduction and FI released large amounts of colloidal Hg, accounting for 44-48% of released Hg. The highest colloidal Hg concentrations at 27.8 and 360µg/L were observed at ∼1 pore volume after FI. Concentration distribution of colloidal OM and colloidal Fe was similar to colloidal Hg in the leachate, showing peak concentrations after IS reduction and FI. Most of the released colloidal Hg was in OM fraction (37-53%), with some in Fe/Mn oxide fraction (11-19%). Based on composition of released colloids and Hg fractionation in soils and colloids, colloidal OM could serve as an important carrier for Hg transport in soils.

Biochar amendment affects leaching potential of copper and nutrient release behavior in contaminated sandy soils.

Copper (Cu) contamination to soil and water is a worldwide concern. Biochar has been suggested to remediate degraded soils. In this study, column leaching and chemical characterization were conducted to assess effects of biochar amendment on Cu immobilization and subsequent nutrient release in Cu-contaminated Alfisol and Spodosol. The results indicate that biochar is effective in binding Cu (30 and 41%, respectively, for Alfisol with and without spiked Cu; 36 and 43% for Spodosol) and reducing Cu leaching loss (from ∼47 to 10% for the Cu-spiked Alfisol and from 48 to 9% for the Cu-spiked Spodosol). Copper was likely retained on biochar surfaces through complexation, as suggested by Fourier-transform infrared spectra. Biochar amendment converts a portion of Cu from available pool to more stable forms, thus resulting in decreased activities of free Cu and increased activity of organic Cu complexes in leachate. Reduction of >0.45-µm solids and nanoparticles concentrations in leachate was also observed. In addition, biochar application rate was correlated negatively with P, Ca, Mg, Zn, Mn, and NH-N concentration ( < 0.05) but positively with K and Na concentration ( < 0.05) in leachates. These results documented the potential of biochar as an effective amendment for Cu immobilization and mitigation of leaching risk for some nutrients.

Phosphorus release from dairy manure, the manure-derived biochar, and their amended soil: effects of phosphorus nature and soil property.

Land application of animal manure often risks excessive phosphorus (P) release into the surrounding water. The aim of this study was to convert the dairy manure into biochar, followed by their application into soil, and then to investigate P release from the manure and its derived biochar as well as from the manure- and biochar-amended soil. The results showed that P release was reduced when the manure was converted into biochar due to formation of less-soluble whitlockite [(Ca, Mg)(PO)]. The cumulative P released from biochar over 240 h was 0.26 g kg, a 76% reduction of that from the manure (1.07 g kg). The kinetic release of P from the manure was determined by the fast desorption process and was better fitted to Elovich equation, whereas P release from biochar was initially controlled by the diffusion process and then by slow but steady dissolution of (Ca,Mg)(PO), following the parabolic diffusion and linear models, respectively. When the manure or biochar was incorporated into the soil, P release in the CaCl and simulated acid rain water extraction from biochar-amended soil was consistently lower than that from the manure-amended soil during 210-d incubation. The lower P release in the biochar-amended soil was determined by stable P form (Ca, Mg)(PO) in the biochar itself, but less from the soil property effect. Results indicated that initial high P release from manure can be mitigated by converting the manure into biochar.

Particulate copper in soils and surface runoff from contaminated sandy soils under citrus production.

Soil contamination by copper (Cu) is a worldwide concern. Laboratory incubation and soil Cu characterization were conducted to examine the effects of external Cu loading and liming on Cu speciation in both bulk soil and particulates of an Alfisol and Spodosol under citrus production. Also, drainage water from the sites was evaluated for dissolved and particulate forms of Cu. Soil available Cu estimated by CaCl2, NH4OAc, or Mehlich-3 extraction significantly increased with external Cu loads and decreased with soil pH. Most increases in soil Cu occurred in the exchangeable and oxide-bound fractions. Organically bound Cu was the dominant fraction in both bulk soil and particulates, but more in particulates than bulk soil (P ≤ 0.001). Organically bound Cu was highly correlated with total recoverable Cu (P ≤ 0.01), increased significantly with external Cu loads (P ≤ 0.001), and decreased with soil pH (P ≤ 0.05). Lime addition converted part of Cu from available pools to more stable forms. Organically bound Cu complexes were found to dominate in soil solution or surface runoff. These results indicate that most Cu accumulated in the contaminated soils is highly mobile, and thus may impact citrus production and the environment.

Orthophosphate Leaching in St. Augustinegrass and Zoysiagrass Grown in Sandy Soil under Field Conditions.

Phosphorus (P) is required to maintain healthy, high-quality, warm-season turf. However, excessive P applications to soils with poor P retention capabilities may lead to leaching losses to groundwater. This field study was conducted to determine the maximum P fertilizer application rate to (Walt.) [Kuntze] 'Floratam' St. Augustinegrass (St. Augustinegrass) and 'Empire' zoysiagrass (zoysiagrass) below which P leaching is minimized. Five P levels ranging from 0 to 5.0 g P m yr were surface applied as triple superphosphate. Turf was established on an uncoated, low-P sand with negligible P retention capacity. Leaf and root growth, tissue P concentration, soil P concentration, soil P saturation, leachate volume, and orthophosphate (P) concentration in leachates were measured. Mehlich 1-extractable soil P (M1-P) and soil P saturation ratio (PSR) increased with time as the P rate increased. Lower M1-P and PSR values were measured with St. Augustinegrass, which absorbed more P than did zoysiagrass. The root system of St. Augustinegrass was larger and deeper compared with zoysiagrass, promoting greater P uptake and less P leaching. If tissue analysis indicates that P fertilization is required and the soil has the capacity to retain additional P, application of 0.8 g P m yr to zoysiagrass and 1.07 g P m yr to St. Augustinegrass is appropriate and does not result in increased P leaching.

Nutrient removal using biosorption activated media: preliminary biogeochemical assessment of an innovative stormwater infiltration basin.

Soil beneath a stormwater infiltration basin receiving runoff from a 23 ha predominantly residential watershed in north-central Florida, USA, was amended using biosorption activated media (BAM) to study the effectiveness of this technology in reducing inputs of nitrogen and phosphorus to groundwater. The functionalized soil amendment BAM consists of a 1.0:1.9:4.1 mixture (by volume) of tire crumb (to increase sorption capacity), silt and clay (to increase soil moisture retention), and sand (to promote sufficient infiltration), which was applied to develop an innovative stormwater infiltration basin utilizing nutrient reduction and flood control sub-basins. Comparison of nitrate/chloride (NO(3)(-)/Cl(-)) ratios for the shallow groundwater indicates that prior to using BAM, NO(3)(-) concentrations were substantially influenced by nitrification or variations in NO(3)(-) input. In contrast, for the new basin utilizing BAM, NO(3)(-)/Cl(-) ratios indicate minor nitrification and NO(3)(-) losses with the exception of one summer sample that indicated a 45% loss. Biogeochemical indicators (denitrifier activity derived from real-time polymerase chain reaction and variations in major ions, nutrients, dissolved and soil gases, and stable isotopes) suggest that NO(3)(-) losses are primarily attributable to denitrification, whereas dissimilatory nitrate reduction to ammonium is a minor process. Denitrification was likely occurring intermittently in anoxic microsites in the unsaturated zone, which was enhanced by the increased soil moisture within the BAM layer and resultant reductions in surface/subsurface oxygen exchange that produced conditions conducive to increased denitrifier activity. Concentrations of total dissolved phosphorus and orthophosphate (PO(4)(3-)) were reduced by more than 70% in unsaturated zone soil water, with the largest decreases in the BAM layer where sorption was the most likely mechanism for removal. Post-BAM PO(4)(3-)/Cl(-) ratios for shallow groundwater indicate predominantly minor increases and decreases in PO(4)(3-) with the exception of one summer sample that indicated a 50% loss. Differences in nutrient variations between the unsaturated zone and shallow groundwater may be the result of the intensity and duration of nutrient removal processes and mixing ratios with water that had undergone little biogeochemical transformation. Observed nitrogen and phosphorus losses demonstrate the potential, as well as the future research needs to improve performance, of the innovative stormwater infiltration basin using BAM for providing passive, economical, stormwater nutrient-treatment technology to support green infrastructure.

Soil property control of biogeochemical processes beneath two subtropical stormwater infiltration basins.

Substantially different biogeochemical processes affecting nitrogen fate and transport were observed beneath two stormwater infiltration basins in north-central Florida. Differences are related to soil textural properties that deeply link hydroclimatic conditions with soil moisture variations in a humid, subtropical climate. During 2008, shallow groundwater beneath the basin with predominantly clayey soils (median, 41% silt+clay) exhibited decreases in dissolved oxygen from 3.8 to 0.1 mg L and decreases in nitrate nitrogen (NO-N) from 2.7 mg L to <0.016 mg L, followed by manganese and iron reduction, sulfate reduction, and methanogenesis. In contrast, beneath the basin with predominantly sandy soils (median, 2% silt+clay), aerobic conditions persisted from 2007 through 2009 (dissolved oxygen, 5.0-7.8 mg L), resulting in NO-N of 1.3 to 3.3 mg L in shallow groundwater. Enrichment of δN and δO of NO combined with water chemistry data indicates denitrification beneath the clayey basin and relatively conservative NO transport beneath the sandy basin. Soil-extractable NO-N was significantly lower and the copper-containing nitrite reductase gene density was significantly higher beneath the clayey basin. Differences in moisture retention capacity between fine- and coarse-textured soils resulted in median volumetric gas-phase contents of 0.04 beneath the clayey basin and 0.19 beneath the sandy basin, inhibiting surface/subsurface oxygen exchange beneath the clayey basin. Results can inform development of soil amendments to maintain elevated moisture content in shallow soils of stormwater infiltration basins, which can be incorporated in improved best management practices to mitigate NO impacts.

Transport and interactions of kaolinite and mercury in saturated sand media.

To evaluate the potential of Hg release and co-transport by colloids, it is important to understand how Hg, colloids and Hg-loaded colloids migrate in soils. Hg sorption by kaolinite and sand were nonlinear and fit the Langmuir model, with the maximum Hg sorption capacity being 1.2mg/g kaolinite and 0.11 mg/g sand. Co-transport of Hg and kaolinite was evaluated using: (1) 1 or 100 mg/L Hg or 100mg/L kaolinite, (2) 1 or 100 mg/L Hg mixed with 100mg/L kaolinite, (3) 1 or 100 mg/L Hg presorbed onto kaolinite, and (4) 25 0mg/L kaolinite in Hg-loaded sand columns. The presence of kaolinite (100 mg/L) reduced Hg's mobility through sand column by increasing deposition rate of Hg-loaded kaolinite. At 100 mg/L Hg, soluble Hg dominated Hg transport; but at 1 mg/L Hg, colloidal Hg (Hg sorbed on kaolinite) affected Hg transport. Preloading 100 mg/L Hg onto kaolinite (0.43 mg/g) reduced kaolinite's mobility with low recovery rate (78%), with Hg retardation (R=1) in Hg-loaded kaolinite being lower than Hg retardation at 100 mg/L Hg (R=1.287). The Hg recovery rate (93%) from Hg-loaded kaolinite at 1mg/L Hg was higher compared to 22% from 1 mg/L Hg. Kaolinite can serve as a carrier to enhance Hg transport in porous media, with 250 mg/L kaolinite mobilizing ~2.4% Hg presorbed onto sand media. Correlation analysis revealed that desorbed Hg was significantly correlated with kaolinite (r=0.81, P<0.0001). Hence kaolinite enhanced Hg transport in the sand media serving both as a carrier (Hg was loaded before transport) and as mobile colloids stripping Hg off the sand media (Hg was loaded during transport).

Simultaneous immobilization of lead and atrazine in contaminated soils using dairy-manure biochar.

Biochar produced from waste biomass is increasingly being recognized as a green, cost-effective amendment for environmental remediation. This work was to determine the ability of biochar to immobilize heavy metal Pb and organic pesticide atrazine in contaminated soils. Biochar prepared from dairy manure was incubated with contaminated soils at rates of 0, 2.5, and 5.0% by weight for 210 d. A commercial activated carbon (AC) was included as a comparison. The AC was effective in immobilizing atrazine, but was ineffective for Pb. However, biochar was effective in immobilizing both atrazine and Pb and the effectiveness was enhanced with increasing incubation time and biochar rates. After 210 d, soils treated with the highest rate of 5.0% biochar showed more than 57% and 66% reduction in Pb and atrazine concentrations in 0.01 M CaCl(2) extraction, respectively. Lead and atrazine concentrations in the toxicity characteristic leaching procedure solutions were reduced by 70-89% and 53-77%, respectively. Uptake of Pb and atrazine by earthworms (Eisenia fetida) was reduced by up to 79% and 73%. Phosphorus originally contained in biochar reacted with soil Pb to form insoluble hydroxypyromorphite Pb(5)(PO(4))(3)(OH), as determined by X-ray diffraction, which was presumably responsible for soil Pb immobilization, whereas atrazine stabilization may result from its adsorption by biochar demonstrated by the significant exponential decrease of extractable atrazine with increasing organic C in biochar (r(2) > 0.97, p < 0.05). The results highlighted the potential of dairy-manure biochar as a unique amendment for immobilization of both heavy metal and organic contaminants in cocontaminated soils.

Spectroscopic models of soil organic carbon in Florida, USA.

Soil organic carbon (SOC) is an indicator of ecosystem quality and plays a major role in the biogeochemical cycles of major nutrients and water. Shortcomings exist to estimate SOC across large regions using rapid and cheap soil sensing approaches. Our objective was to estimate SOC in 7120 mineral and organic soil horizons in Florida using visible/near-infrared diffuse reflectance spectroscopy (VNIRS) calibrated by committee trees and partial least squares regression (PLSR). The derived VNIRS models were validated using independent datasets and explained up to 71 and 38% of the variance of SOC in mineral and organic horizons, respectively. We stratified the mineral horizons into seven soil orders and derived PLSR models for each order, which explained from 32% (Histosols) to 75% (Ultisols) of the variance of SOC concentration in validation mode. Estimates of SOC from all models were highly scattered along the regression lines, especially for high SOC values, and the slopes of the regression lines were generally <1 because VNIRS models tended to underestimate high SOC values and overestimate low SOC. Despite the great scatter of estimates in the prediction plots, VNIRS models had reasonable explanatory power for mineral horizons, given the heterogeneity of soils and environmental conditions in Florida, and have potential for the rapid assessment of SOC, with implications for regional SOC assessments, modeling, and monitoring. However, VNIRS models for organic horizons were hampered by small sample size and had very limited explanatory power.

Properties of dairy-manure-derived biochar pertinent to its potential use in remediation.

Conversion of waste products into biochar (BC) is being considered as one of several waste disposal and recycling options. In this study, we produced BC from dairy manures by heating at low temperatures (500 degrees C) and under abundant air condition. The resultant BC was characterized for physical, chemical, and mineralogical properties specifically related to its potential use in remediation. The BC from all manures behaved similarly. Surface area, ash content, and pH of the BC increased as temperature increased, while yield decreased with increasing temperature. The BC was rich in mineral elements such as N, Ca, Mg, and P in addition to C, and concentrations of C and N decreased with increasing temperature as a result of combustion and volatilization; while P, Ca, and Mg increased as temperature increased. For example, C significantly decreased from 36.8% at 100 degrees C to 1.67% at 500 degrees C; whereas P increased from 0.91% to 2.66%. Water soluble P, Ca, and Mg increased when heated to 200 degrees C but decreased at higher temperatures likely due to increased crystallization of Ca-Mg-P, as supported by the formation of whitlockite (Ca,Mg)(3)(PO(4))(2) following 500 degrees C treatment. The presence of whitlockite was evidenced by X-ray diffraction analysis. Quartz and calcite were present in all BC produced. The BC showed appreciable capability of adsorption for Pb and atrazine from aqueous solution, with Pb and atrazine removal by as high as 100% and 77%, respectively. The results indicated that dairy manure can be converted into biochar as an effective adsorbent for application in environmental remediation.