Fractionation and mobility of phosphorus in a sandy forest soil amended with biosolids

Goal, Scope and Background Biosolids, i.e., treated sewage sludge, are commonly used as a fertilizer and amendment to improve soil productivity. Application of biosolids to meet the nitrogen (N) requirements of crops can lead to accumulation of phosphorus (P) in soils, which may result in P loss to water bodies. Since 1996, biosolids have been applied to a Pinus radiata D. Don plantation near Nelson City, New Zealand, in an N-deficient sandy soil. To investigate sustainability of the biosolids application programme, a long-term research trial was established in 1997, and biosolids were applied every three years, at three application rates, including control (no biosolids), standard and high treatments, based on total N loading. The objective of this study was to evaluate the effect of repeated application of biosolids on P mobility in the sandy soil. Materials and Methods Soil samples were collected in August 2004 from the trial site at depths of 0–10, 10–25, 25–50, 50–75, and 75–100 cm. The soil samples were analysed for total P (TP), plant-available P (Olsen P and Mehlich 3 P), and various P fractions (water-soluble, bioavailable, Fe and Al-bound, Ca-bound, and residual) using a sequential P fractionation procedure. Results and Discussion Soil TP and Olsen P in the high biosolids treatment (equivalent to 600 kg N ha⁻¹ applied every three years) had increased significantly (P<0.05) in both 0–10 cm and 10–25 cm layers. Mehlich 3 P in soil of the high treatment had increased significantly only at 0–10 cm. Olsen P appeared to be more sensitive than Mehlich 3 P as an indicator of P movement in a soil profile. Phosphorus fractionation revealed that inorganic P (Al/Fe-bound P and Ca-bound P) and residual P were the main P pools in soil, whereas water-soluble P accounted for approximately 70% of TP in biosolids. Little organic P was found in either the soil or biosolids. Concentrations of water-soluble P, bioavailable inorganic P (NaHCO₃ Pi) and potentially bioavailable inorganic P (NaOH Pi) in both 0–10 and 10–25 cm depths were significantly higher in the high biosolids treatment than in the control. Mass balance calculation indicated that most P applied with biosolids was retained by the top soil (0–25 cm). The standard biosolids treatment (equivalent to 300 kg N ha⁻¹ applied every three years) had no significant effect on concentrations of TP, Mehlich 3 P and Olsen P, and P fractions in soil. Conclusions The results indicate that the soil had the capacity to retain most biosolids-derived P, and there was a minimal risk of P losses via leaching in the medium term in the sandy forest soil because of the repeated biosolids application, particularly at the standard rate. Recommendations and Perspectives Application to low-fertility forest land can be used as an environmentally friendly option for biosolids management. When biosolids are applied at a rate to meet the N requirement of the tree crop, it can take a very long time before the forest soil is saturated with P. However, when a biosolids product contains high concentrations of P and is applied at a high rate, the forest ecosystem may not have the capacity to retain all P applied with biosolids in the long term. ESS-Submission Editor: Dr. Jean-Paul Schwitzguébel jean-paul.schwitzguebel@epfl.ch     

Kinetics of the reduction of hexavalent chromium with the brown seaweed Ecklonia biomass

The dead biomass of the brown seaweed, Ecklonia sp., is capable of reducing toxic Cr(VI) into less toxic or nontoxic Cr(III). However, little is known about the mechanism of Cr(VI) reduction by the biomass. The objective of this work was to develop a kinetic model for Cr(VI) biosorption, for supporting our mechanism. The reduction rate of Cr(VI) increased with increasing total chromate concentration, [Cr(VI)], and equivalent concentration of organic compounds, [OCs], and decreasing solution pH. It was found that the reduction rate of Cr(VI) was proportional to [Cr(VI)] and [OCs], suggesting the simple kinetic equation -d[Cr(VI)]/dt=k[Cr(VI)][OCs]. When considering the consumption of organic compounds due to the oxidation by Cr(VI), an average rate coefficient of 9.33 (+/-0.65)microM(-1)h(-1) was determined, at pH 2. Although the function of the pH could not be expressed in a mechanistic manner, an empirical model able to describe the pH dependence was obtained. It is expected that the developed rate equation could likely be used for design and performance predictions of biosorption processes for treating chromate wastewaters.     

Occurrence and accumulation patterns of polycyclic aromatic hydrocarbons and synthetic musk compounds in adipose tissues of Korean females

Very few studies have reported on the occurrence and accumulation profiles of polycyclic aromatic hydrocarbons (PAHs) and synthetic musk compounds (SMCs) in human adipose tissue. In this study, concentrations of PAHs and SMCs in adipose tissues collected from Korean women in 2007 and 2008 were determined. Total concentrations of PAHs and SMCs in adipose tissues ranged from 15 to 361 (mean: 119) ng g^-1 lipid weight and from 38 to 253 (mean: 106) ng g^-1 lipid weight, respectively. Concentrations of SMCs in Korean adipose tissues were lower than those reported for European countries and the United States. Naphthalene was the most predominant PAH and HHCB was the dominant SMC found in adipose tissues. The concentrations of PAHs and SMCs were not correlated with each other, suggesting that the sources of human exposure to these two classes of compounds are different. No correlation was found between donor’s age and residue levels of PAHs and SMCs. The results of this study provide baseline information on exposure of PAHs and SMCs to the general population in Korea.     

Effects of polychlorinated biphenyls on whole animal energy mobilization and hepatic cellular respiration in rainbow trout, Oncorhynchus mykiss

The production of polychlorinated biphenyls (PCBs) was banned in 1977 but these chemicals persist in the environment and threaten aquatic organisms. PCB exposure often results in activation of the aryl hydrocarbon receptor (AhR) and increases in hepatic detoxification mechanisms. Activation of these detoxification mechanisms is believed to be associated with energetic demands that may come at the expense of other physiological processes such as growth, activity and reproduction. We tested the hypothesis that exposure to sub-lethal levels of PCBs results in increased energy demand and energy mobilization using both an in vivo and in vitro approach. Rainbow trout (Oncorhynchus mykiss) received a single intraperitoneal sub-lethal dose (50 μg kg⁻¹) of 3,3’,4,4’,5-pentachlorobiphenyl (PCB 126) and left for 10 d after which standard oxygen consumption and plasma and liver metabolites were assessed. PCB 126 exposed trout did not alter standard oxygen consumption but did increase plasma glucose concentration implying the mobilization of glucose to cope with this exposure regime. Cellular respiration was assessed in trout hepatocytes exposed to PCB 126 or PCB 77 (3,3′4,4′-tetrachlorobiphenyl) two AhR activators but with different potencies (PCB 126 ? PCB 77). Mitochondrial respiration was assessed by stimulating complex II with succinate and although no increases in respiration were associated with PCB exposure in non-stimulated cells, PCB 77 impaired mitochondrial respiration by preventing stimulation of complex II respiration and potentially masking any actual energetic costs of PCB exposure. These studies suggest that energy is mobilized upon exposure to PCBs, however, actual increases in energy demand may be overshadowed by impaired mitochondrial respiration.     

Evaluating Flow Diversion Impacts to Groundwater‐Dependent Riparian Vegetation with Flow Alteration and Groundwater Model Analysis

An approach for assessing the potential ecologic response of groundwater‐dependent riparian vegetation to flow alteration is developed, focusing on change to groundwater. Groundwater requirements for riparian vegetation are reviewed in conjunction with flow alteration statistics. Where flow alteration coincides with groundwater‐related vegetation sensitivities, scenarios are developed for groundwater simulation. Groundwater depths and recession rates in the riparian zone are simulated for baseline and altered stream hydrographs, with changes to river stage and width represented with a transient, flow‐dependent boundary condition. Potential flow diversion from the Upper Gila River in New Mexico is examined. Statistical flow alteration analysis, applying prospective diversions to a 76‐year record of daily flow, shows that flows in the winter‐spring months and within the high‐pulse to small flood range are subject to greatest potential change. Groundwater simulation scenarios are developed for these flow conditions in representative dry, near‐average, and wet years. Differences in groundwater elevations, generally less than 0.25 m during the flow alteration period, dissipate rapidly following cessation of diversion. Relating groundwater depth, recession rates and range of fluctuations to riparian vegetation needs, we find adverse ecological response is not expected from groundwater impacts for the flow alteration examined.     

Modeling adsorption kinetics of trichloroethylene onto biochars derived from soybean stover and peanut shell wastes

Trichloroethylene (TCE) is one of the most hazardous organic pollutants in groundwater. Biochar produced from agricultural waste materials could serve as a novel carbonaceous adsorbent for removing organic contaminants from aqueous media. Biochars derived from pyrolysis of soybean stover at 300 °C and 700 °C (S-300 and S-700, respectively), and peanut shells at 300 °C and 700 °C (P-300 and P-700, respectively) were utilized as carbonaceous adsorbents to study batch aqueous TCE remediation kinetics. Different rate-based and diffusion-based kinetic models were adopted to understand the TCE adsorption mechanism on biochars. With an equilibrium time of 8–10 h, up to 69 % TCE was removed from water. Biochars produced at 700 °C were more effective than those produced at 300 °C. The P-700 and S-700 had lower molar H/C and O/C versus P-300 and S-300 resulting in high aromaticity and low polarity accompanying with high surface area and high adsorption capacity. The pseudo-second order and intraparticle diffusion models were well fitted to the kinetic data, thereby, indicating that chemisorption and pore diffusion were the dominating mechanisms of TCE adsorption onto biochars.     

Immobilization of lead in contaminated firing range soil using biochar

Soybean stover-derived biochar was used to immobilize lead (Pb) in military firing range soil at a mass application rate of 0 to 20 wt.% and a curing period of 7 days. The toxicity characteristic leaching procedure (TCLP) was performed to evaluate the effectiveness of the treatment. The mechanism responsible for Pb immobilization in military firing range soil was evaluated by scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray absorption fine structure (XAFS) spectroscopy analyses. The treatment results showed that TCLP Pb leachability decreased with increasing biochar content. A reduction of over 90 % in Pb leachability was achieved upon treatment with 20 wt.% soybean stover-derived biochar. SEM-EDX, elemental dot mapping and XAFS results in conjunction with TCLP leachability revealed that effective Pb immobilization was probably associated with the pozzolanic reaction products, chloropyromorphite and Pb-phosphate. The results of this study demonstrated that soybean stover-derived biochar was effective in immobilizing Pb in contaminated firing range soil.     

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3

TiO₂-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH₃ with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn⁴⁺, displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO₂ catalysts were important for the low-temperature SCR at 80～160 and 200～350 °C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO₂ oxidation at low temperatures.

Implications: Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO_x). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO₂ catalysts.     

Biodegradability and biodegradation rate of poly(caprolactone)-starch blend and poly(butylene succinate) biodegradable polymer under aerobic and anaerobic environment

The biodegradability and the biodegradation rate of two kinds biodegradable polymers; poly(caprolactone) (PCL)-starch blend and poly(butylene succinate) (PBS), were investigated under both aerobic and anaerobic conditions. PCL-starch blend was easily degraded, with 88% biodegradability in 44 days under aerobic conditions, and showed a biodegradation rate of 0.07 day⁻¹, whereas the biodegradability of PBS was only 31% in 80 days under the same conditions, with a biodegradation rate of 0.01 day⁻¹. Anaerobic bacteria degraded well PCL-starch blend (i.e., 83% biodegradability for 139 days); however, its biodegradation rate was relatively slow (6.1 mL CH₄/g-VS day) compared to that of cellulose (13.5 mL CH₄/g-VS day), which was used as a reference material. The PBS was barely degraded under anaerobic conditions, with only 2% biodegradability in 100 days. These results were consistent with the visual changes and FE-SEM images of the two biodegradable polymers after the landfill burial test, showing that only PCL-starch blend had various sized pinholes on the surface due to attack by microorganisms. This result may be use in deciding suitable final disposal approaches of different types of biodegradable polymers in the future.     

Nutrients and Heavy Metals in Legacy Sediments: Concentrations,Comparisons with Upland Soils,and Implications for Water Quality

Concentrations of nutrients and heavy metals in streambank legacy sediments are needed to estimate watershed exports and to evaluate against upland inputs. Concentrations of nutrients and heavy metals were determined for legacy sediments in 15 streambanks across northeastern Maryland, southeastern Pennsylvania, and northern Delaware. Samples were collected from multiple bank depths from forested, agricultural, urban, and suburban sites. Analyses were performed for fine (<63 μm) and coarse sediment fractions. Nutrient and heavy metal concentrations were significantly higher in fine than coarse legacy sediments and water extractable nutrient concentrations were significantly greater for fine sediments. Nutrient and heavy metal concentrations were highest in streambank legacy sediments associated with urban land use, but few differences were found with bank depth. Total N (40–3,970 mg/kg) and P (25–1,293 mg/kg) and bioavailable P (0.25–48.8 mg/kg) concentrations for legacy sediments were lower than those for upland soils. This suggests that legacy sediments could serve as sink or source of N and P depending on the redox conditions and stream water nutrient concentrations. However, despite low concentrations, caution should be exercised since streambank erosion and legacy sediment mass loadings could be high, these sediments are in immediate proximity of aquatic ecosystems, and biogeochemical transformations could result in release of the nutrients.