Modeling the competitive sorption and transport of Ni(II) and Zn(II) in soils: Comparing two multicomponent approaches.

The mobility of contaminants in soil is controlled by sorption reactions which can be affected by the presence of other solutes that compete for sorption sites. The ability to model such effects is necessary for evaluating the environmental risk of a given contaminant. In this study, the competitive sorption and transport of nickel (Ni) and zinc (Zn) in Olivier and Windsor soils was investigated using batch equilibration and miscible displacement experiments. During batch experiments, the sorption of Ni and Zn was mutually reduced in multicomponent systems, indicating that the metal cations compete for sorption sites. When applied concurrently, the retardation of both ions decreased and peak effluent concentrations increased relative to single ion experiments, demonstrating that competition increased the mobility of both ions during miscible displacement experiments. A novel Freundlich-type multicomponent isotherm (CDI) and its kinetic analog (CDIT) were developed and compared to the commonly used SRS isotherm and SRS-based kinetic approach (SRST) in describing the experimental data. The CDI provided a superior description of the competitive batch data, especially at low surface coverage, and may therefore be more applicable to multicomponent sorption than the SRS. The Olivier and Windsor transport data were best described by the CDIT and SRST, respectively, however, both models generally described the data well. Since both approaches gave comparable descriptions of the transport data while the CDI outperformed the SRS in describing the batch data, the CDI/CDIT may be more generally applicable to multicomponent systems and warrants further study.

Modeling the sorption of Ni(II) and Zn(II) by Mn oxide-coated sand: Equilibrium and kinetic approaches.

The behavior of metal cations in oxide-dominated systems is controlled by sorption reactions, which in turn depend on pH. Descriptions of such reactions are of interest for contaminant monitoring or remediation efforts; however, widely used isotherms such as Freundlich or Langmuir neglect the effect of pH and are therefore limited in their applicability. Two pH-dependent isotherms and their kinetic analogs were developed and evaluated regarding their ability to describe equilibrium and time-dependent sorption of Ni and Zn by Mn oxide-coated sand (MOCS). The sorption of Ni and Zn by MOCS at pH 4.0, 5.5, and 7.0 was investigated using batch equilibration and stirred-flow techniques. The affinity of MOCS for either metal cation was highly pH dependent, with greater affinity at higher pH. Both isotherms described the batch data well. Flow interruption during stirred-flow experiments indicated that chemical nonequilibrium existed between solution and sorbed phases of both Ni and Zn and that such nonequilibrium was greater with increasing pH. Both kinetic models provided good descriptions of the solution data from stirred-flow experiments and correctly captured the effect of pH on chemical nonequilibrium. These models offer simple alternatives to surface complexation approaches and are expected to be easily applied to describe equilibrium and time-dependent sorption of a wide range of metal cations by variably charged minerals or oxide-coated media.

Remediation of crude oil-contaminated coastal marsh soil: Integrated effect of biochar, rhamnolipid biosurfactant and nitrogen application.

Decontamination of oil spills from coastal wetland soils requires a delicate approach. A microcosm study was carried out to investigate the impact of integrated application of biochar, rhamnolipid (RL) biosurfactant and nitrogen (N) on petroleum hydrocarbon remediation in a Louisiana coastal saline marsh and their impact on soil microbial community. The soil was artificially contaminated with crude oil and subjected to treatments of different combinations of sugarcane residue biochar, RL, and coated urea. Total petroleum hydrocarbons (TPH) in the contaminated soil were analyzed periodically using gas chromatograph and associated soil bacterial community was studied using 16 s rRNA sequencing technologies. Results showed that integrated application of biochar + RL, biochar + N, and biochar + N+RL reduced 32.3%, 73.2%, 80.9% of TPH, respectively, and exhibited synergic interaction with higher efficiency than application individually. Combined treatments showed distinct functions that biochar increased the sorption of aromatic compounds, while RL and N enhanced the degradation of heavy and light aliphatic compounds. All remediation treatments caused reduction of soil bacterial diversity while RL and N shifted the microbial community to higher abundances of Proteobacteria and Bacteroidetes, respectively. Overall, the findings of this study demonstrate the positivity of applying integrated biochar, biosurfactant, and N treatment in oil remediation in wetland soils.

Potential use of biochar and rhamnolipid biosurfactant for remediation of crude oil-contaminated coastal wetland soil: Ecotoxicity assessment.

Remediation of wetland soils contaminated with petroleum hydrocarbons is a challenging task. Biosurfactant and biochar have been used in oil remediation. However, little is known about the ecotoxicity of these materials when applied in wetland ecosystems. In this study, the ecotoxicity of biochar and rhamnolipid (RL) biosurfactant as crude oil remediation strategies in a Louisiana wetland soil was investigated. A pot experiment was set up with wetland soil treated with/without crude oil followed by subjecting to application of 1% biochar and various levels of RL ranging from 0.1% to 1.4%. The ecotoxicity was evaluated regarding to high plant (S. Alterniflora), algae, and soil microbes. Specifically, after a 30-day growth in a controlled chamber, plant biomass change as well as shoot/root ratio was measured. Algae growth was estimated by quantifying chlorophyll by spectrometry following separation, and soil microbial community was characterized by phospholipid fatty acids analysis. Results showed that plant can tolerate RL level up to 0.8%, while algae growth was strongly inhibited at RL > 0.1%. Algal biomass was significantly increased by biochar, which offset the negative impact of oil and RL. Additionally, soil microbial community shift caused by crude oil and RL was alleviated by biochar with promoting Gram-positive bacteria, actinomycetes, and arbuscular mycorrhizal fungi. Overall, this study shows that integrated treatment of biochar and RL has the lowest ecotoxicity to plant and algae when used in oil remediation of contaminated wetland soils.

Exploring anaerobic CO2 production response to elevated nitrate levels in Gulf of Mexico coastal wetlands: Phenomena and relationships.

Recent studies have shown the effect of nitrate (NO3-) on carbon gas emissions from wetland soils that contradict thermodynamic predictions. In this study, CO2 production in three Mississippi River deltaic plain wetland soils (forest swamp, freshwater and saline marshes) with the presence of different NO3- levels (0.2, 2.0, and 3.2 mM) was evaluated in an anaerobic microcosm. Molecular composition of dissolved organic matter (DOM) of these soils was investigated using pyrolysis-GC/MS, and soil microbial community was characterized based on phosphorus lipid fatty acid (PLFA) method to elucidate the underlying mechanisms. Addition of NO3- promoted CO2 production in swamp forest soil, but inhibited CO2 emission from marsh soils. Pyrolysis-GC/MS analysis showed that swamp soil contained more polysaccharides, whereas both marsh soils had high abundance of phenolic compounds. Total PLFAs of forest swamp soil were 34% and 66% higher than freshwater and saline marsh soils, respectively. The PLFA profiles indicated different microbial distribution along a salinity gradient with the forest swamp having a higher proportion of fungi and NO3- reducers but lower sulfate (SO42-) reducers than marsh soils. Overall, the study indicated that the inherent differences in soil DOM and microbial community led to the contrasting response in soil CO2 respiration between forest swamp and marsh ecosystems to NO3- loading. These differences should be considered in determining the fate of nitrate entering Louisiana coastal wetlands from river diversions and other sources and their management.

Sorption and Desorption Characteristics of Tylosin in Three Louisiana Soils.

The macrolide antibiotic tylosin is widely used in animal production, but its environmental fate is not fully understood. Objectives of this study were to determine the effect of pH on tylosin A sorption and desorption in three sandy loam soils from Louisiana, USA, that had long histories of poultry waste application, to model sorption and desorption, and to estimate the effect of high soil organic matter on sorption. Twenty-four-hour sorption isotherms (5 to 200 mg L in 0.01 M CaCl) at pH 4.5, 6.0, and pH 7.5 were described by the Freundlich model. Desorption from the 200-mg L set at constant pH by 10 24-h extractions with 0.01 M CaCl recovered 43 to 98% of the added tylosin A, and further desorption with methanol increased recovery from 66 to 100%. Single-point distribution coefficient, as a function of pH from 4 to 9 in 0.01 M CaCl exhibited maxima from pH 6 to 7, reflecting increasing sorption of the positively charged form with increasing pH up to about the pKa. The data were well described, modeling pH-dependent negative charge according to Henderson-Hasselbalch along with tylosin speciation. Using soil from which organic matter had been removed by HO gave three to six times greater K at pH 6 to 7, but without or with reduced maxima. The data could be approximately described without invoking pH-dependent surface charge. Further study is needed to confirm whether an increase in soil organic matter with poultry waste application decreases tylosin sorption, thus increasing environmental risk.

Facilitative capture of As(V), Pb(II) and methylene blue from aqueous solutions with MgO hybrid sponge-like carbonaceous composite derived from sugarcane leafy trash.

Enhancing the contaminant adsorption capacity is a key factor affecting utilization of carbon-based adsorbents in wastewater treatment and encouraging development of biomass thermo-disposal. In this study, a novel MgO hybrid sponge-like carbonaceous composite (HSC) derived from sugarcane leafy trash was prepared through an integrated adsorption-pyrolysis method. The resulted HSC composite was characterized and employed as adsorbent for the removal of negatively charged arsenate (As(V)), positively charged Pb(II), and the organic pollutant methylene blue (MB) from aqueous solutions in batch experiments. The effects of solution pH, contact time, initial concentration, temperature, and ionic strength on As(V), Pb(II) and MB adsorption were investigated. HSC was composed of nano-size MgO flakes and nanotube-like carbon sponge. Hybridization significantly improved As(V), Pb(II) and methylene blue (MB) adsorption when compared with the material without hybridization. The maximum As(V), Pb(II) and MB adsorption capacities obtained from Langmuir model were 157 mg/g, 103 mg/g and 297 mg/g, respectively. As(V) adsorption onto HSC was best fit by the pseudo-second-order model, and Pb(II) and MB with the intraparticle diffusion model. Increased temperature and ionic strength decreased Pb(II) and MB adsorption onto HSC more than As(V). Further FT-IR, XRD and XPS analysis demonstrated that the removal of As(V) by HSC was mainly dominated by surface deposition of MgHAsO4 and Mg(H2AsO4)2 crystals on the HSC composite, while carbon π-π* transition and carbon π-electron played key roles in Pb(II) and MB adsorption. The interaction of Pb(II) with carbon matrix carboxylate was also evident. Overall, MgO hybridization improves the preparation of the nanotube-like carbon sponge composite and provides a potential agricultual residue-based adsorbent for As(V), Pb(II) and MB removal.

Biochar produced from mineral salt-impregnated chicken manure: Fertility properties and potential for carbon sequestration.

In this study, nutrient properties and carbon sequestration potential of biochars derived from chicken manure (CM) impregnated with mineral salts (calcium chloride, magnesium chloride, ferric chloride) were evaluated. Pretreatment with mineral salts reduced phosphorus (P) availability via the formation of insoluble metal phosphate minerals. Less carbon was lost during the pyrolysis of pretreated CM, and the produced biochars (BCCa, BCMg, and BCFe) were more stable (i.e., reduced C loss during chemical oxidation and less CO2 release during incubation) than pristine biochars. Spectroscopic evidence indicated that enhanced biochar stability via metal salt pretreatment before pyrolysis was related to increased aromatization and enhanced physical protection due to the metal-oxygen interaction, together with the formation of metal mineral phases on biochar surfaces. Moreover, ferric chloride was the optimal additive, as it significantly decreased biochar P leachability and increased carbon sequestration potential.

Enhancing phosphate adsorption by Mg/Al layered double hydroxide functionalized biochar with different Mg/Al ratios.

Mg/Al ratio plays a significant role for anion adsorption by Mg/Al-layered double hydroxides (Mg/Al-LDHs) modified biochar. In this study, Mg/Al-LDHs biochar with different Mg/Al ratios (2, 3, 4) were prepared by co-precipitation for phosphate removal from aqueous solution. Factors on phosphate adsorption including Mg/Al ratio, pH, and the presence of other inorganic anions were investigated through batch experiments. Increasing Mg/Al ratio in the Mg/Al-LDHs biochar composites generally enhanced phosphate adsorption with Langmuir adsorption maximum calculated at 81.83mg phosphorous (P) per gram of 4:1Mg/Al-LDHs biochar at pH3.0. The adsorption process was best described by the pseudo-second-order kinetic model. Solution pH had greater effects on the phosphate adsorption by Mg/Al LDHs biochar composites with lower Mg/Al ratios. The presence of other inorganic anions decreased the phosphate adsorption efficiency in the order of F(-) > SO4(2-) > NO2(-) >Cl(-). Phosphate adsorption mechanism involves ion exchange, electrostatic attraction and surface inner-sphere complex formation. Overall, Mg/Al-LDHs biochar composites offer a potential alternative of carbon-based adsorbent for phosphate removal from aqueous solution.

Losses of surface runoff, total solids, and nitrogen during bermudagrass establishment on levee embankments.

Nutrient and sediment runoff from newly constructed levee embankments pose a threat to water quality during soft armor vegetation establishment. Research was initiated in 2008 and 2009 to evaluate the effect of bermudagrass ( L.) coverage and N source on nutrient and sediment runoff from levee embankments during establishment. Bermudagrass plots were seeded at 195.3 kg pure live seed ha and fertilized at 50 kg N ha using a water-soluble N source, urea or NH-NO, or slow-release N source, S-coated urea (SCU) or urea formaldehyde (UF), with controls unfertilized. Vegetative cover percentage, time until the onset of runoff, runoff volume, and total solids (TS), NO-N, and NH-N concentrations were measured from simulated and natural rainfall events for 70 d in 2008 and 56 d in 2009. Bermudagrass at 90% grass cover delayed the onset of runoff an additional 441 to 538 s and reduced runoff volumes 74 to 84% of that exhibited at 10% grass cover. Nitrogen fertilizers did not accelerate bermudagrass growth sufficiently, however, to reduce TS loading compared with unfertilized bermudagrass in either year of the study. The application of urea and SCU resulted in cumulative N losses of 2.45 and 3.13 kg ha compared with 1.59 kg ha from the unfertilized bermudagrass in 2008, and 1.73 kg ha from NH-NO vs. 0.24 kg ha from controls in 2009. Only UF increased bermudagrass establishment without increasing cumulative N losses compared with unfertilized bermudagrass. Therefore, the benefit of greater erosion and runoff resistance expected from N-accelerated vegetative growth did not occur but had the unintended consequence of higher N losses when water-soluble N and SCU fertilizers were applied.

Nutrient dynamics and tree growth of silvopastoral systems: impact of poultry litter.

Fertilizing pastures with poultry litter has led to an increased incidence of nutrient-saturated soils, particularly on highly fertilized, well drained soils. Applying litter to silvopastures, in which loblolly pine (Pinus taeda L.) and bahiagrass (Paspalum notatum) production are integrated, may be an ecologically desirable alternative for upland soils of the southeastern USA. Integrating subterranean clover (Trifolium subterraneum) into silvopastures may enhance nutrient retention potential. This study evaluated soil nutrient dynamics, loblolly pine nutrient composition, and loblolly pine growth of an annually fertilized silvopasture on a well drained soil in response to fertilizer type, litter application rate, and subterranean clover. Three fertilizer treatments were applied annually for 4 yr: (i) 5 Mg litter ha(-1) (5LIT), (ii) 10 Mg litter ha(-1) (10LIT), and (iii) an inorganic N, P, K pasture blend (INO). Litter stimulated loblolly pine growth, and neither litter treatment produced soil test P concentrations above runoff potential threshold ranges. However, both litter treatments led to accumulation of several nutrients (notably P) in upper soil horizons relative to INO and unfertilized control treatments. The 10LIT treatment may have increased N and P leaching potential. Subterranean clover kept more P sequestered in the upper soil horizon and conferred some growth benefits to loblolly pine. Thus, although these silvopasture systems had a relatively high capacity for nutrient use and retention at this site, litter should be applied less frequently than in this study to reduce environmental risks.

Phosphorus runoff relationships for Louisiana Coastal Plain soils amended with poultry litter.

Long-term application of poultry (Gallus gallus domesticus) litter has built high levels of P in certain Coastal Plain soils of north Louisiana. However, soil P/runoff P relationships for soil and environmental conditions of the area have not been examined. This study measured soil P (total, Bray 1, Bray 2, Mehlich 3, resin-exchangeable, and water-extractable) and runoff P (dissolved P, DP; and total P, TP) at four pasture sites previously amended with poultry litter. Sites varied in soil P due to annual litter applications ranging from 1 to more than 20. Three replicated plots at each site were subjected to simulated rainfalls over 2 yr, and concentrations of DP and TP in runoff were measured and related to soil P. This allowed examination of soil P/runoff P relationships and their changes over time. Runoff DP was also related to DP desorbed from surface soil in a miscible displacement experiment. Among measures of soil P, only resin-exchangeable and water-extractable P showed significant decreases over 2 yr. These measures of soil P explained 54 to 64% of the variability in runoff DP data. However, the miscible displacement technique proved the best indicator of runoff DP, explaining 70% of the variability. Runoff varied among sites (decreasing with increasing years of litter application), limiting the predictive capability of the soil extraction methods. Linking runoff characteristics with miscible displacement data may be a useful predictive tool and warrants further examination.