Phenanthrene accumulation kinetics in marine diatoms

Cell surface and intracellular accumulation kinetics of phenanthrene were studied in two coastal marine diatoms. Cell surface uptake and depuration rate constants were two to three times greater in the smaller Thalassiosira pseudonana than in T. weissflogii, reflecting the 2.8-fold difference in surface-area-to-volume ratio (A/V) between the two species. However, cell surface accumulation was faster than most other environmental and biological process, supporting the assumption that cell surfaces are in equilibrium with the water. Intracellular depuration rate constants of phenanthrene were similar (0.56 d(-1), 0.62 d(-1)) for both diatoms and for other hydrophobic organic contaminants (ca 1 d(-1)) with a range of hydrophobicities and chemical structures in other microalgae. Biodilution could be a significant factor in the internal accumulation of phenanthrene, as phenanthrene loss rate constants were on the order of phytoplankton growth rates in the spring and summer (1-3 d(-1)). Organic carbon-normalized phenanthrene bioconcentration factors were not significantly different for the two diatom species. The fraction of phenanthrene in the cell surface compartment at steady-state (x1) was directly related to the A/V of the two diatoms and a Chlorophyte microalga, showing that intracellular partitioning, which may affect phenanthrene trophic transfer, depends on phytoplankton cell size.     

Mechanistic characterization of adsorption and slow desorption of phenanthrene aged in soils

Long-term adsorption of phenanthrene to soils was characterized in a silt-loam (LHS), a sandy soil (SBS), and a podzolized soil (CNS) by use of the Polanyi-Manes model, a Langmuir-type model, and a black carbon-water distribution coefficient (K(BC)) at a relative aqueous concentration (C(e)/S(w)) of 0.002-0.32. Aqueous desorption kinetic tests and temperature-programmed desorption (TPD) were also used to evaluate phenanthrene diffusivities and desorption activation energies. Adsorption contribution in soils was 48-70% after 30 days and 64-95% after 270 days. Significant increases in adsorption capacity with aging suggest that accessibility of phenanthrene to fractions of SBS soil matrix was controlled by sorptive diffusion at narrow meso- and micropore constrictions. Similar trends were not significant for LHS silt-loam or CNS podzol. Analysis of TPD profiles reveal desorption activation energies of 35-53 kJ/mol and diffusivities of 1.6 x 10(-7-)9.7 x 10(-8) cm2/s. TPD tests also indicate that the fraction of phenanthrene mass not diffusing from soils was located within micropores and narrow width mesopores with a corresponding volume of 1.83 x 10(-5-)6.37 x 10(-5) cm3/g. These values were consistent with the modeled adsorption contributions, thus demonstrating the need for such complimentary analytical approach in the risk assessment of organic contaminants.     

Formation of organic iodine supplied as iodide in a soil-water system in Chiba, Japan

Speciation of iodine in a soil-water system was investigated to understand the mechanism of iodine mobility in surface environments. Iodine speciation in soil and pore water was determined by K-edge XANES and HPLC-ICP-MS, respectively, for samples collected at a depth of 0-12 cm in the Yoro area, Chiba, Japan. Pore water collected at a 0-6 cm depth contained 50%-60% of organic iodine bound to dissolved organic matter, with the other portion being I(-). At a 9-12 cm depth, 98% of iodine was in the form of dissolved I(-). In contrast, XANES analysis revealed that iodine in soil exists as organic iodine at all depths. Iodine mapping of soil grains was obtained using micro-XRF analysis, which also indicated that iodine is bound to organic matter. The activity of laccase, which has the ability to oxidize I(-) to I(2), was high at the surface of the soil-water layer, suggesting that iodide oxidizing enzymes can promote iodine organification. The distribution coefficient of organic iodine in the soil-water system was more than 10-fold greater than that of iodide. Transformation of inorganic iodine to organic iodine plays an important role in iodine immobilization, especially in a surface soil-water system.     

Engineered polymeric nanoparticles for bioremediation of hydrophobic contaminants

Sorption of hydrophobic organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), to soil has been shown to limit their solubilization rate and mobility. In addition, sequestration of contaminants by sorption to soil and by partitioning in nonaqueous phase liquids (NAPLs) reduces their bioavailability. Polymeric nano-network particles have been demonstrated to increase the "effective" solubility of a representative hydrophobic organic contaminant, phenanthrene (PHEN) and to enhance the release of PHEN from contaminated aquifer material. In this study, we investigate the usefulness of nanoparticles made from a poly(ethylene) glycol modified urethane acrylate (PMUA) precursor chain, in enhancing the bioavailability of PHEN. PMUA nanoparticles are shown to increase the mineralization rate of PHEN crystal in water, PHEN sorbed on aquifer material, and PHEN dissolved in a model NAPL (hexadecane) in the presence of aquifer media. These results show that PMUA particles not only enhance the release of sorbed and NAPL-sequestered PHEN but also increase its mineralization rate. The accessibility of contaminants in PMUA particles to bacteria also suggests that particle application may be an effective means to enhance the in-situ biodegradation rate in remediation through natural attenuation of contaminants. In pump-and-treat or soil washing remediation schemes, bioreactors could be used to recycle extracted nanoparticles. The properties of PMUA nanoparticles are shown to be stable in the presence of a heterogeneous active bacterial population, enabling them to be reused after PHEN bound to the particles has been degraded by bacteria.     

Lead sequestration and species redistribution during soil organic matter decomposition

The turnover of soil organic matter (SOM) maintains a dynamic chemical environment in the forest floor that can impact metal speciation on relatively short timescales. Here we measure the speciation of Pb in controlled and natural organic (O) soil horizons to quantify changes in metal partitioning during SOM decomposition in different forest litters. We provide a link between the sequestration of pollutant Pb in O-horizons, estimated by forest floor Pb inventories, and speciation using synchrotron-based X-rayfluorescence and X-ray absorption spectroscopy. When Pb was introduced to fresh forest O(i) samples, it adsorbed primarily to SOM surfaces, but as decomposition progressed over two years in controlled experiments, up to 60% of the Pb was redistributed to pedogenic birnessite and ferrihydrite surfaces. In addition, a significant fraction of pollutant Pb in natural soil profiles was associated with similar mineral phases (approximately 20-35%) and SOM (-65-80%). Conifer forests have at least 2-fold higher Pb burdens in the forest floor relative to deciduous forests due to more efficient atmospheric scavenging and slower organic matter turnover. We demonstrate that pedogenic minerals play an important role in surface soil Pb sequestration, particularly in deciduous forests, and should be considered in any assessment of pollutant Pb mobility.     

Modeling kinetics of Cu and Zn release from soils

Kinetics of Cu and Zn release from soil particles was studied using two surface soils with a stirred-flow method. Different solution pH, dissolved organic matter (DOM) concentrations, and flow rates were tested in this study. A model for kinetics controlled sorption/desorption reactions between soils and solutions was globally fit to all experimental data simultaneously. Results were compared to a model that assumes local instantaneous equilibrium. We obtained one unique set of model parameters applicable to different pH, dissolved organic carbon (DOC), and flow conditions. We included DOM complexation of copper ions, which decreased their sorption. The effect of pH was included by assuming proton competition with metal ions for binding sites on soil particles. These results provide the basis for developing predictive models for metal release from soil particles to surface waters and soil solution.     

Significance of iron(II,III) hydroxycarbonate green rust in arsenic remediation using zerovalent iron in laboratory column tests

We examined the corrosion products of zerovalent iron used in three column tests for removing arsenic from water under dynamic flow conditions. Each column test lasted 3-4 months using columns consisting of a 10.3-cm depth of 50:50 (w:w, Peerless iron:sand) in the middle and a 10.3cm depth of a sediment from Elizabeth City, NC, in both upper and lower portions of the 31-cm-long glass column (2.5 cm in diameter). The feeding solutions were 1 mg of As(V) L(-1) + 1 mg of As(III) L(-1) in 7 mM NaCl + 0.86 mM CaSO4 with or without added phosphate (0.5 or 1 mg of P L(-1)) and silicate (10 or 20 mg of Si L(-1)) at pH 6.5. Iron(II,III) hydroxycarbonate green rust (or simply, carbonate green rust) and magnetite were the major iron corrosion products identified with X-ray diffraction for the separated fractions (5 and 1 min sedimentation and residual). The presence of carbonate green rust was confirmed by scanning electron microscopy (hexagonal morphology) and FTIR-photoacoustic spectroscopy (interlayer carbonate stretching mode at 1352-1365 cm(-1)). X-ray photoelectron spectroscopy investigation revealed the presence of predominantly As(V) at the surface of corroded iron particles despite the fact that the feeding solution in contact with Peerless iron contained more As(III) than As(V) as a result of a preferential uptake of As(V) over As(III) by the Elizabeth City sediment. Extraction of separated corrosion products with 1.0 M HCI showed that from 86 to 96% of the total extractable As (6.9-14.6 g kg(-1)) was in the form of As(V) in agreement with the XPS results. Combined microscopic and macroscopic wet chemistry results suggest that sorbed As(III) was partially oxidized by the carbonate green rust at the early stage of iron corrosion. The column experiments suggest that either carbonate green rust is kinetically favored or is thermodynamically more stable than sulfate green rust in the studied Peerless iron corrosion systems.     

Ambivalent role of water in thermodesorption of hydrocarbons from contaminated soil

Thermodesorption studies with soil samples from a former filling station for light crude oil contaminated with mineral oil hydrocarbons (mainly benzene, toluene, ethylbenzene, xylenes, naphthalene, alkylnaphthalenes, and C(10) to C(14) alkanes) have revealed an ambivalent influence of water on desorption rates. Particularly, the influences of soil moisture content, humidity of the purge gas, temperature, and content of soil organic matter (SOM) were studied. At low temperature, purge gas humidity strongly affected the mobility of hydrocarbons in the soil organic matter (SOM) leading to an enhanced release of contaminants at higher moisture contents. Heating resulted in a decrease of thermodesorption when connected with desiccation of soil, in spite of the strong temperature impact on the vapor pressure of contaminants. At high water content of the SOM, the transfer of the pollutant molecules into the gas phase was found to be markedly hindered by the formation of water films or pore-filling by bulk water, both acting as diffusion barriers.     

Chloride and organic chlorine in forest soils: storage, residence times, and influence of ecological conditions

Recent studies have shown that extensive chlorination of natural organic matter significantly affects chlorine (Cl) residence time in soils. This natural biogeochemical process must be considered when developing the conceptual models used as the basis for safety assessments regarding the potential health impacts of 36-chlorine released from present and planned radioactive waste disposal facilities. In this study, we surveyed 51 French forested areas to determine the variability in chlorine speciation and storage in soils. Concentrations of total chlorine (Cl(tot)) and organic chlorine (Cl(org)) were determined in litterfall, forest floor and mineral soil samples. Cl(org) constituted 11-100% of Cl(tot), with the highest concentrations being found in the humus layer (34-689 mg Cl(org) kg(-1)). In terms of areal storage (53 - 400 kg Cl(org) ha(-1)) the mineral soil dominated due to its greater thickness (40 cm). Cl(org) concentrations and estimated retention of organochlorine in the humus layer were correlated with Cl input, total Cl concentration, organic carbon content, soil pH and the dominant tree species. Cl(org) concentration in mineral soil was not significantly influenced by the studied environmental factors, however increasing Cl:C ratios with depth could indicate selective preservation of chlorinated organic molecules. Litterfall contributions of Cl were significant but generally minor compared to other fluxes and stocks. Assuming steady-state conditions, known annual wet deposition and measured inventories in soil, the theoretical average residence time calculated for total chlorine (inorganic (Cl(in)) and organic) was 5-fold higher than that estimated for Cl(in) alone. Consideration of the Cl(org) pool is therefore clearly important in studies of overall Cl cycling in terrestrial ecosystems.     

Sorption nonlinearity for organic contaminants with diesel soot: method development and isotherm interpretation

An experimentally practical and precise flocculation-based method was developed, tested, and applied to determine phenanthrene and 1,2,4-trichlorobenzene sorption with NIST SRM 2975 diesel particulate matter. Following an initial equilibration period, polyaluminum chloride (PACI) solution was added to the sorption tubes in order to facilitate the formation of flocculated aggregates of soot particles. After separation of the solids through centrifugation, supernatant concentrations were determined as with conventional batch methods. The flocculation-based method was tested on three kinds of soot and then used to evaluate sorption kinetics and equilibrium with SRM 2975. Kinetic results showed that wetting of the soot required more than 20 days, but that 60 days was sufficient to achieve equilibration with both water and phenanthrene. Sixty-day isotherms for both phenanthrene and 1,2,4-trichlorobenzene were strongly nonlinear. At approximate 10(-3) of solubility, carbon-normalized distribution coefficients (Koc) were 10-20 times higher than those for absorption to sediment organic matter. Measurements at closer to solubility indicated much lower Koc, suggesting a total sorption capacity at aqueous solubility that is of similar magnitude to that in sediment organic matter. Independent analysis of extractable hydrocarbons suggests that absorption into a native hydrocarbon phase was not a major component of sorption.     

Distributed reactivity model for sorption by soils and sediments. 15. High-concentration co-contaminant effects on phenanthrene sorption and desorption

Soil and sediment materials having organic matter matrixes of different geochemical character were examined with respect to their sorption and desorption of phenanthrene in the presence of order-of-magnitude larger concentrations of trichloroethylene (TCE) and dichlorobenzene (DCB). These co-contaminants depressed phenanthrene sorption in the lowest residual solution phase concentration ranges of that target solute investigated, whereas in its highest residual concentration regions phenanthrene sorption was either not affected or was actually enhanced. In both concentration ranges, the effects observed varied with the hydrophobicity and relative concentration of the co-contaminant and with the geological maturity and associated degree of condensation and aromatization of the soil/sediment organic matter (SOM). Desorption isotherms for phenanthrene indicate the occurrence of increased hysteresis in the presence of high concentrations of DCB and TCE, the effect increasing with increased degree of associated organic condensation. Tests in which high concentrations of DCB and TCE were added after completion of the phenanthrene desorption experiments show clear evidence of partial displacement of sorbed phenanthrene to the solution phase. The results of the work support the concept of SOM glass-transition concentrations, above which matrix deformation occurs and so-called "conditioning effects" are observed.     

Chloride retention and release in a boreal forest soil: effects of soil water residence time and nitrogen and chloride loads

The common assumption that chloride (Cl-) is conservative in soils and can be used as a groundwater tracer is currently being questioned, and an increasing number of studies indicate that Cl- can be retained in soils. We performed lysimeter experiments with soil from a coniferous forest in southeast Sweden to determine whether pore water residence time and nitrogen and Cl- loads affected Cl- retention. Over the first 42 days there was a net retention of Cl- with retention rates averaging 3.1 mg CI- m(-2) d(-1) (68% of the added Cl- retained over 42 days). Thereafter, a net release of Cl- at similar rates was observed for the remaining experimental period (85 d). Longer soil water residence time and higher Cl- load gave higher initial retention and subsequent release rates than shorter residence time and lower Cl- load did. Nitrogen load did not affect Cl transformation rates. This study indicates that simultaneous retention and release of Cl- can occur in soils, and that rates may be considerable relative to the load. The retention of Cl- observed was probably due to chlorination of soil organic matter or ion exchange. The cause of the shift between net retention and net release is unclear, but we hypothesize that the presence of O2 or the presence of microbially available organic matter regulates Cl- retention and release rates.     

Enhancing phenanthrene biomineralization in a polluted soil using gaseous toluene as a cosubstrate

Laboratory experiments were conducted to study the potential of adding gaseous toluene, as a readily degradable carbon source, to enhance phenanthrene mineralization in polluted soil (1,000 mg/kg(dry soil)) aged for 400 days. Experiments were conducted in 0.5-L column reactors packed with a mixture of (80:20 w(wet)/w(wet)) spiked soil and vermiculite and fed with 1 g m(-3)reactor h(-1) toluene load in air. Removal efficiencies of 100% for toluene and greater than 95% for phenanthrene were obtained in 190 h. Evolved CO2 showed that phenanthrene mineralization increased from 39% to 86% in columns treated with gaseous toluene. Phthalic acid was identified as the principal soluble intermediate, which accumulated when no toluene was added. Increased phenanthrene uptake and mineralization with toluene can be attributed to increased biomass and the induction of enzymes involved in the intermediate mineralization. In microcosm experiments, phthalic acid mineralization increased from 19% to 81% within 50 h in the presence of toluene. Experiments with 14C-labeled phenanthrene confirmed the enhancement of phenanthrene mineralization from 45% to 83% in 385 h with toluene as a second carbon source. The results indicate thatthe addition of an appropriate gaseous cosubstrate could be an adequate strategy to enhance mineralization of PAHs in soil.     

深耕配施有机肥对云南保山植烟土壤肥力的快速提升效应

为研究土壤耕作深度与有机肥对植烟土壤肥力的快速提升效果,设置3种耕作深度（S1：深耕10cm;S2：深耕20cm;S3：深耕30cm）与2种有机肥（OF：商品有机肥;FM：农家肥）的交互试验,研究一个生长季内不同处理对土壤物理结构、养分变化及酶活性的影响。结果表明：（1）耕作深度与有机肥种类对土壤物理特性无显著影响。二者互作可显著提高0~20和20~40cm土层土壤有机质含量。S3FM可显著提高0~20cm土层土壤有机质、全氮和硝态氮含量及20~40cm土层土壤有机质的含量。（2）耕作深度×有机肥种类可显著影响0~20和20~40cm土层脲酶活性。S1FM较S1OF显著提高0~20和20~40 cm土层蔗糖酶活性41.75%和14.29%;当均施用农家肥时,脲酶的活性在耕深30cm达到最高,较其他处理增幅最高达57.89%。（3）土壤肥力质量综合评价表明,S3FM处理0~20和20~40cm土层土壤肥力质量得分均最高,分别为0.58与0.74。可见,农家肥深耕30cm可实现在一个生长季内提升保山植烟土壤肥力质量的目的。     

A distributed reactivity model for sorption by soils and sediments 13. Simulated diagenesis of natural sediment organic matter and its impact on sorption/desorption equilibria

Subcritical water treatment was used to effect rapid compositional and functional changes to peat organic matter that mimic those of the natural diagenesis process. Elemental, solid state 13C NMR, FTIR, and calorimetry analyses all indicated that the organic matter of the artificially aged peat was chemically similar to that of geologically mature coal kerogens. This paper extends the work of the previous paper in this series, which investigated the effects of subcritical water treatment of humic topsoil on subsequent phenanthrene sorption and desorption equilibria. As opposed to the previous study, however, changes in sorptive reactivity herein were unequivocally related to changes in organic matter rather than other soil constituents, and organic matter functional changes due to the simulated diagenesis were more accurately characterized. Phenanthrene sorption capacity and isotherm nonlinearity both increased with increasing degrees of artificial aging, supporting the viewpoint that hydrophobic organic contaminant sorption equilibrium properties can be directly related to the degree of diagenesis of geosorbent organic matter. In addition, this work investigated effects of subcritical water treatment of a geologically mature, kerogen-containing shale sample. In contrast to the peat, the functional characteristics of the shale were unchanged by this treatment, and subsequent phenanthrene sorption equilibria were altered far less.     

Facilitating effects of metal cations on phenanthrone sorption in soils

Effects of metal cations (Na+, Ca2+, and Al3+) on phenanthrene sorption were investigated using two soils with contrasting organic carbon (OC) contents. The presence of the polyvalent cations (i.e., Ca2+ or Al3+) at a concentration of 0.01 mol/L significantly increased the capacity and nonlinearity of phenanthrene sorption to soils compared with the monovalent Na+. The effects were governed by the content of soil OC. Rubbery OC (i.e., soft, amorphous OC including dissolved organic carbon (DOC)) tended to become condensed on soil surfaces as evidenced by a decrease in the signals of the 1H NMR spectra of DOC and an increase in the glass transition temperature (Tg) of the soils when the polyvalent cations were present. Increasing Ca2+ concentration led initially to an effect similar to that of the polyvalent cations in the low cation concentration range, and the effect was gradually attenuated as Ca2+ concentration further increased. These findings lead us to propose that the modifications in the physical configuration and chemical characteristics of OC resulting from the presence of metal cations account for the increase in the capacity and nonlinearity of phenanthrene sorption to the soils. This study points to an important role of metal cations in the sorption and fate of phenanthrene in the soil environment.     

Optimizing contaminant desorption and bioavailability in dense slurry systems. 2. PAH bioavailability and rates of degradation

The effects of mechanical mixing on rates of polycyclic aromatic hydrocarbon (PAH) biodegradation in dense geosorbent slurry (67% solids content, w/w) systems were evaluated using laboratory-scale intermittently mixed batch bioreactors. A PAH-contaminated soil and a phenanthrene-sorbed mineral sorbent (alpha-Al2O3) were respectively employed as slurry solids in aerobic and anaerobic biodegradation studies. Both slurries exhibited a characteristic behavior of pseudoplastic non-Newtonian fluids, and the impeller revolution rate and its diameter had dramatic impacts on power and torque requirements in their laminar flow mixing. Rates of phenanthrene biodegradation were markedly enhanced by relatively low-level auger mixing under both aerobic and anaerobic (denitrifying) conditions. Parameters for empirical models correlating biodegradation rate coefficient (k(b)) values to the degree of mixing were similar to those for correlations between mass transfer (desorption) rate coefficient (k(r)) values for rapidly desorbing fractions of soil organic matter and degree of mixing reported in a companion study, supporting a conclusion that performance-efficient and cost-effective enhancements of PAH mass transfer (desorption) and its biodegradation processes can be achieved by the introduction of optimal levels of reactor-scale mechanical mixing.     

A chemical extraction method for mimicking bioavailability of polycyclic aromatic hydrocarbons to wheat grown in soils containing various amounts of organic matter

In this study, we have evaluated the extent to which organic matter contents in soils influence the accumulation of PAHs by the roots of wheat plants and have developed a rapid chemical method for determining the bioavailability of PAH. Four polycyclic aromatic hydrocarbons (PAHs), naphthalene, acenaphthylene, fluorene, and phenanthrene, were added to natural soil samples with different amounts of organic matterfor pot experiments to evaluate apparent bioavailability of PAHs to wheat roots (Triticum aestivum L.). The extractabilities of PAHs in the soil were tested by a sequential extraction scheme using accelerated solvent extraction with water, n-hexane, and a mixture of dichloromethane and acetone as solvents. The water or n-hexane-extractable PAHs were positively correlated to dissolved organic matter (DOM) and negatively correlated to total organic matter (TOM), indicating mobilization and immobilization effects of DOM and TOM on soil PAHs, respectively. The apparent accumulation of PAHs by wheat roots was also positively and negatively correlated to DOM and TOM, respectively. As a result, there are positive correlations between the amounts of PAHs extracted by water or n-hexane and the quantities accumulated in plant roots, suggesting the feasibility of using water- or n-hexanes-extractable fractions as indicators of PAH availability to plants.     

Impact of black carbon in the extraction and mineralization of phenanthrene in soil

During the past century, increased biomass burning and fossil fuel consumption have drastically increased the input of black carbon (BC) into the environment, and that has been shown to influence the behavior of organic contaminants in soil. A study was conducted to investigate the effects of BC on the relationship between aqueous hydroxypropyl-beta-cyclodextrin (HPCD) extraction and microbial mineralization (bioaccessibility) of 14C-phenanthrene (10 mg kg(-1)) in four soils amended with 0, 0.1, 0.5, 1, 2.5, and 5% (% dry wt soil) activated charcoal, a type of BC. Mineralisation was monitored over 20 d incubation, within respirometric assays, using an inoculum containing a phenanthrene-degrading pseudomonad and compared to HPCD extraction (24 h) using 50 mM aqueous solution; analyses were conducted after 1, 25, 50, and 100 d soil-phenanthrene contact time. Statistical analyses revealed that for each soil the addition of BC led to significant (P < 0.001) reductions in both HPCD extractability and microbial mineralization. Linear correlations for BC concentrations of 0% (r2 = 0.95; slope = 0.89) and 0.1% (r2 = 0.67; slope = 0.95) revealed a highly significant (P < 0.01) relationship between HPCD extractability and total mineralization (20 d), indicating a direct prediction of phenanthrene bioaccessibility by HPCD. However, in soils amended with 0.5, 1, 2.5, and 5% BC exhibited r2 values ranging 0.51-0.13 and slopes of 2.19-12.73. This study has shown that BC strongly sorbs phenanthrene causing reductions in extractability and, to a lesser extent, bioaccessibility to degrading microorganisms.