Interaction of latex colloids with mineral surfaces and Grimsel granodiorite

Bentonite clay is considered as possible backfill material for nuclear waste repositories in crystalline rock. The same material may also be a source of clay colloids, which may act as carriers for actinide ions possibly released from the repository. Depending on the geochemical parameters, these colloids may be retained by interaction with mineral surfaces of the host rock. In the present study interaction of carboxylated fluorescent latex colloids, used as a model for bentonite colloids, with natural Grimsel granodiorite and some of its component minerals is studied by fluorescence microscopy and SEM/EDX. The experiments are carried out by varying the pH from 2–10. Strong adsorption is observed at pH values close to or below the points of zero charge (pH_pzc) of the mineral surfaces. The influence of Eu(III), used as a chemical homologue for trivalent actinide ions, on colloid adsorption is investigated. Depending on mineral phase and pH, a significant increase of colloid adsorption is observed in the presence of Eu(III).     

Review of the complexation of tetravalent actinides by ISA and gluconate under alkaline to hyperalkaline conditions

Isosaccharinic (ISA) and gluconic acids (GLU) are polyhydroxy carboxylic compounds showing a high affinity to metal complexation. Both organic ligands are expected in the cementitious environments usually considered for the disposal of low- and intermediate-level radioactive wastes. The hyperalkaline conditions imposed by cementitious materials contribute to the formation of ISA through cellulose degradation, whereas GLU is commonly used as a concrete additive. Despite the high stability attributed to ISA/GLU complexes of tetravalent actinides, the number and reliability of available experimental studies is still limited. This work aims at providing a general and comprehensive overview of the state of the art regarding Th, U(IV), Np(IV), and Pu(IV) complexes with ISA and GLU.In the presence of ISA/GLU concentrations in the range 10^− 5–10^− 2 M and absence of calcium, An(IV)(OH)_x(L)_y complexes (An(IV) = Th, U(IV), Np(IV), Pu(IV); L = ISA, GLU) are expected to dominate the aqueous speciation of tetravalent actinides in the alkaline pH range. There is a moderate agreement among their stability, although the stoichiometry of certain An(IV)-GLU complexes is still ill-defined. Under hyperalkaline conditions and presence of calcium, the species CaTh(OH)₄(L)₂(aq) has been described for both ISA and GLU, and similar complexes may be expected to form with other tetravalent actinides.In the present work, the available thermodynamic data for An(IV)–ISA/GLU complexes have been reviewed and re-calculated to ensure the internal consistency of the stability constants assessed. Further modelling exercises, estimations based on Linear Free-Energy Relationships (LFER) among tetravalent actinides, as well as direct analogies between ISA and GLU complexes have also been performed. This approach has led to the definition of a speciation scheme for the complexes of Th, U(IV), Np(IV) and Pu(IV) with ISA and GLU forming in alkaline to hyperalkaline pH conditions, both in the absence and presence of calcium.     

A generalised sorption model for the concentration dependent uptake of caesium by argillaceous rocks

A three-site cation exchange model is proposed to describe the concentration dependent uptake of Cs on natural argillaceous rock systems. Major premises in the model are that the sorption of Cs is dominated by the illite mineral component in the rock and that there is a fixed relationship between the site capacities of the three site types denoted as frayed edge, type II and planar sites. The definition of a “reference illite” with a cation exchange capacity of 0.2 equiv. kg^-1 allows the three site capacities to be fixed in the model calculations over the weight fraction of illite in the argillaceous rocks. Up to Cs equilibrium concentrations of 10^-3 M sorption occurs predominantly on the frayed edge and type II sites (higher affinity sites), with the planar site type playing only a minor role. Competition with Cs for sorption on the former two site types arises predominantly from monovalent cations such as K, Rb and NH₄ which have low hydration energies. H and Na (except at high concentrations) are considerably less competitive and bivalent cations such as Mg, Ca and Sr are effectively non-competitive. A consistent set of selectivity coefficients for Cs with respect to K, Rb, NH₄ and Na was derived from analyses and modelling of a wide range of Cs sorption data available in the open literature on pure illites from many different sources. The model was tested against four Cs sorption isotherm data sets determined on argillaceous rocks: Boom clay, Oxford clay, Palfris marl and Opalinus clay. The water chemistries and illite contents given in these experiments allowed the Cs sorption isotherms to be predicted. It is concluded that the Cs sorption model presented here, in which there are no free parameters, can be used to predict the uptake of Cs at equilibrium concentrations below 10^-3 M to within a factor of 2 to 3 in natural argillaceous rock systems.     

Comparative studies of the Fe–UV, H2O2–UV, TiO2–UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.     

Sorption–desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions

Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd_ads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kf_ads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ～800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n_ads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.     

Coupled infrared extinction spectra and size distribution measurements for several non-clay components of mineral dust aerosol (quartz, calcite, and dolomite)

Simultaneous size distributions and Fourier transform infrared (FTIR) extinction spectra have been measured for several representative components of mineral dust aerosol (quartz, calcite, and dolomite) in the fine particle size mode (D=0.1–1 μm). Optical constants drawn from the published literature have been used in combination with the experimentally determined size distributions to simulate the extinction spectra. In general, Mie theory does not accurately reproduce the peak position or band shape for the prominent IR resonance features in the 800–1600 cm⁻¹ spectral range. The resonance peaks in the Mie simulation are consistently blue shifted relative to the experimental spectra by 20–50 cm⁻¹. Spectral simulations, derived from a simple Rayleigh-based analytic theory for a “continuous distribution of ellipsoids” particle shape model, better reproduce the experimental spectra, despite the fact that the Rayleigh approximation is not strictly satisfied in these experiments. These results differ from our previous studies of particle shape effects in silicate clay mineral dust aerosols where a disk-shaped model for the particles was found to be more appropriate.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

Adsorption of chlorpyrifos,penconazole and metalaxyl from aqueous solution by modified clays

Sorption of three pesticides (chlorpyrifos, metalaxyl and penconazole) has been measured on a commercial clay montmorillonite and on the same mineral modified with either of two cationic-surfactant micelles. Both micelle–clay complexes, commercial names Cloisite 20A and Cloisite 30B, showed a good capacity to sorb all three pesticides from water, whereas their sorption on the natural montmorillonite was not described by an isotherm. Modelling sorption on both micelle–clay complexes showed that the Freundlich sorption constant (K _F) was higher for chlorpyrifos on Cloisite 20A (K _F = 7.76) than on Cloisite 30B (K _F = 5.91), whereas the sorption of metalaxyl was stronger on Cloisite 30B (K _F = 1.07) than on Cloisite 20A (K _F = 0.57). Moreover the micelle–clay complex Cloisite 20A also showed a good affinity for penconazole, the maximum quantity adsorbed (q _m) of 6.33 mg g^?1 being 45% more than that on Cloisite 30B. Single-batch adsorption of each pesticide onto both micelle–clay complexes was studied using the Freundlich isotherm for chlorpyrifos and metalaxyl and the Langmuir isotherm for penconazole. The Cloisite 20A micelle–clay complex was predicted to require 23% less adsorbent to treat certain volumes of wastewater containing 30 mg L^?1 chlorpyrifos, 43% more to treat metalaxyl similarly and 57% less to treat penconazole compared with Cloisite 30B.     

Neptunium(V) adsorption to calcite

The migration behavior of the actinyl ions U(VI)O₂²⁺, Np(V)O₂⁺ and Pu(V,VI)O₂^(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO₂⁺ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO₂ partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased K_D values after desorption compared to adsorption.     

Natural and anthropogenic factors affecting the groundwater quality in the Nandong karst underground river system in Yunan, China

The Nandong Underground River System (NURS) is located in a typical karst agriculture dominated area in the southeast Yunnan Province, China. Groundwater plays an important role for social and economical development in the area. However, with the rapid increase in population and expansion of farm land, groundwater quality has degraded. 42 groundwater samples collected from springs in the NURS showed great variation of chemical compositions across the study basin. With increased anthropogenic contamination in the area, the groundwater chemistry has changed from the typical Ca–HCO₃ or Ca (Mg)–HCO₃ type in karst groundwater to the Ca–Cl (+ NO₃) or Ca (Mg)–Cl (+ NO₃), and Ca–Cl (+ NO₃ + SO₄) or Ca (Mg)–Cl (+ NO₃ + SO₄) type, indicating increases in NO₃⁻, Cl⁻ and SO₄²⁻ concentrations that were caused most likely by human activities in the region. This study implemented the R-mode factor analysis to investigate the chemical characteristics of groundwater and to distinguish the natural and anthropogenic processes affecting groundwater quality in the system. The R-mode factor analysis together with geology and land uses revealed that: (a) contamination from human activities such as sewage effluents and agricultural fertilizers; (b) water–rock interaction in the limestone-dominated system; and (c) water–rock interaction in the dolomite-dominated system were the three major factors contributing to groundwater quality. Natural dissolution of carbonate rock (water–rock interaction) was the primary source of Ca²⁺ and HCO₃⁻ in groundwater, water–rock interaction in dolomite-dominated system resulted in higher Mg²⁺ in the groundwater, and human activities were likely others sources. Sewage effluents and fertilizers could be the main contributor of Cl⁻, NO₃⁻, SO₄²⁻, Na⁺ and K⁺ to the groundwater system in the area. This study suggested that both natural and anthropogenic processes contributed to chemical composition of groundwater in the NURS, human activities played the most important role, however.     

Modelling of silica diffusion experiments with Si in Boom Clay

A mathematical model describing the dissolution of nuclear glass directly disposed in clay combines a first-order dissolution rate law with the diffusion of dissolved silica in clay. According to this model, the main parameters describing the long-term dissolution of the glass are ηR, the product of the diffusion accessible porosity η and the retardation factor R, and the apparent diffusion coefficient D_app of dissolved silica in clay.For determining the migration parameters needed for long-term predictions, four Through-Diffusion (T-D) experiments and one percolation test have been performed on undisturbed clay cores. In the Through-Diffusion experiments, the concentration decrease after injection of ³²Si (radioactive labelled silica) was measured in the inlet compartment. At the end of the T-D experiments, the clay cores were cut in thin slices and the activity of labelled silica in each slice was determined. The measured activity profiles for these four clay cores are well reproducible.Since no labelled silica could be detected in the outlet compartments, the Through-Diffusion experiments are fitted by two In-Diffusion models: one model assuming linear and reversible sorption equilibrium and a second model taking into account sorption kinetics. Although the kinetic model provides better fits, due to the sufficiently long duration of the experiments, both models give approximately similar values for the fit parameters. The single percolation test leads to an apparent diffusion coefficient value about two to three times lower than those of the Through-Diffusion tests.Therefore, dissolved silica appears to be strongly retarded in Boom Clay. A retardation factor R between 100 and 300 was determined. The corresponding in situ distribution coefficient K_d is in the range 25–75 cm³ g⁻¹. The apparent diffusion coefficient of dissolved silica in Boom Clay is estimated between 2×10⁻¹³ and 7×10⁻¹³ m² s⁻¹. The pore diffusion coefficient is in the range from 6×10⁻¹¹ to 1×10⁻¹⁰ m² s⁻¹.     

Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg⁻¹) compared to soil B (22.03 mg kg⁻¹). The simazine adsorption distribution coefficients (K_d) were 9.32 L kg⁻¹ for soil A and 7.74 L kg⁻¹ for soil B. The simazine adsorption enthalpy in soil A was −21.0 kJ mol⁻¹ while in soil B the adsorption enthalpy value was −11.5 kJ mol⁻¹. These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine–organic matter interactions and in soil B by simazine–clay interactions. The understanding of simazine sorption–desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.     

In vitro assessment of AhR-mediated activities of TCDD in mixture with humic substances

Humic substances (HS) are ubiquitous natural products of decomposition of dead organic matter. HS is present in most freshwaters at concentrations ranging from 0.5 to 50 mg L⁻¹. Organic carbon can represent 20% dry weight of sediments. Recently, the interaction of dissolved HS with the aryl hydrocarbon receptor (AhR) has been demonstrated. The AhR is a cytosolic receptor to which persistent organic pollutants (POPs) can bind and many of their toxic effects are mediated through interactions with this receptor. We describe in vitro effects (using H4IIE-luc cells) of binary mixtures of various HS with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), since in contaminated environments these compounds occur simultaneously. Six out of 12 HS samples activated AhR even at environmentally relevant concentrations (17 mg L⁻¹), but did not reach the full AhR-activation even at excessive concentration. In simultaneous exposure of H4IIE-luc to HS (17 mg L⁻¹) and TCDD (1.2 pM) without any preincubation prior to exposure, either significant additive or facilitative effects were observed. No negative interactions, due to possible sorption of TCDD to HS was observed. Nevertheless, if the HS–TCDD binary mixture was preincubated for 6 days prior to the exposure on H4IIE-luc cells, the additive and facilitative effects were less due to possible sorption of TCDD onto HS. Similar results were obtained from analogous experiments with greater concentrations of both TCDD and HS.     

Sorption of heterocyclic compounds from a complex mixture of coal-tar compounds on natural clayey till

The sorption and desorption of heterocyclic organic compounds in a complex multisolute system to a natural clayey till was investigated. The composition of the solutes reflect a simplified composition of an aqueous phase in contact with coal tar. Sorption was studied for two ratios (s:l) of clayey till (solid) to aqueous phase (liquid). The effect of the complex mixture of solutes on sorption of the four heterocyclic compounds: benzofuran, dibenzofuran, benzothiophene, and dibenzothiophene is evaluated by comparison with their sorption measured in single-solute systems. Sorption of the four compounds is affected by the complex mixture, with sorption decreases for all four compounds at high s:l ratio indicating competitive sorption. The effect on sorption of the individual compounds is not related to solubility or hydrophobicity of the compounds. Freundlich-type isotherms are observed for all compounds in the high s:l-ratio experiments, but for the most hydrophobic compounds isotherms are close to linear. The sorption of N-compounds and benzofuran is apparently influenced by cation exchange and dipole–dipole attraction to clay minerals. At high concentrations a dramatic increase in the sorption of the most strongly sorbing compounds is observed in the low s:l-ratio experiment. The dramatic increase in sorption appears to be a result of multimolecular layer sorption or condensation on surfaces in the clayey till at high surface density of organic compounds, and the data are fitted by BET (Brunauer, Emmet, and Teller) type 2 isotherms. The increase may or may not be induced by the presence of N-heterocyclic compounds sorbed by cation exchange and dipole–dipole attraction. The desorption of the compounds was studied for the low s:l ratio where multimolecular layer formation apparently had occurred. Partially irreversible sorption, hysteric Langmuir type desorption with isotherms of very high K_l coefficient, or behaviour reflecting dissolution of a condensed phase is observed.     

Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

Development of steady-state phosphate concentrations in septic system plumes

Long-term monitoring of PO₄⁻³ behaviour in a well-defined septic system plume on calcareous sand (Cambridge site) shows that, after 17 yr of system operation, a distinct PO₄⁻³ plume (PO₄⁻³−P > 1 mg L⁻¹) is present extending 20 m downgradient from the infiltration bed. The PO₄³⁻ plume migration velocity is 1 m yr⁻¹, reflecting retardation by a factor of 20 compared to the groundwater velocity. During monitoring between years 10 to 17, an expanding steady-state zone was noted below the infiltration bed where PO₄³⁻ −P levels remained consistently near 4 mg L⁻¹, a value 25% lower than the average effluent value (6.3 mg L⁻¹). The pattern of attenuation — a 25% mass loss in the 2-m-thick vadose zone, then little further attenuation along the flowpath — is suggestive of a condition of equilibrium with a controlling phosphate mineral phase. Chemical equilibrium modelling shows supersaturation with respect to hydroxylapatite and variscite. Four other field sites are identified from the literature and from our work where similar steady-state PO₄³⁻ zones are present in septic system plumes. In these, steady-state levels range from 15% to 68% of effluent values, with lower concentrations observed in the more acidic plumes, again indicative of a mineral solubility control, possibly variscite.PO₄³⁻ behaviour in these plumes suggests that, although P migration velocity is controlled by the processes of sorption, the magnitude of PO₄³⁻ that is present is governed by the constraints of phosphate mineral solubility. When septic systems on sands are located relatively close to sensitive surface water bodies and when long-term downgradient impact is the primary concern, more attention should be focused on the geochemical conditions that control PO₄³⁻ mineral solubility rather than only on the sorption characteristics of the sediment.     

Diffusion of tritiated water and Na through non-degraded hardened cement pastes

Diffusion experiments through hardened cement pastes (HCP) using tritiated water (HTO) and ²²Na⁺, considered to be conservative tracers, have been carried out in triplicates in a glove box under a controlled nitrogen atmosphere. Each experiment consisted of a through-diffusion test followed by an out-diffusion test.The experimental data were inversely modelled applying an automated Marquardt–Levenberg procedure. The analysis of the through-diffusion data allowed the extraction of values for the effective diffusion coefficients, D_e, and the rock capacity factor, α. Good agreement between measured and calculated tracer breakthrough curves was achieved using both a simple diffusion model without sorption and a diffusion/linear sorption model. The best-fit K_d-values were found to be consistent with R_d-values measured in previous batch-sorption experiments.The best-fit values from the through-diffusion tests were then used to predict the results of subsequent out-diffusion experiments. Good agreement between experimental data and predictions was achieved only for the case of linear sorption.Isotopic exchange can only partially account for both the amount of tracer taken up in the batch-sorption tests and the measured retardation in the diffusion experiments and, hence, additional mechanisms have to be invoked to explain the data.     

Nitric oxide emission from a typical vegetable field in the Pearl River Delta, China

Croplands contribute to atmospheric nitric oxide (NO), but very limited data are available about NO fluxes from intensively managed croplands in China. In this study, NO fluxes were measured in a typical vegetable field planted with flowering Chinese cabbage (Brassica campestris L. ssp. Chinensis var. utilis Tsen et Lee), which is the most widely cultivated vegetable in Guangdong province, south China. NO emission drastically increased after nitrogen fertilizer application, and other practices involving loosening the soil also enhanced NO emission. Mean NO emission flux was 47.5 ng N m⁻² s^–1 over a complete growth cycle. Annual NO emission from the vegetable field was about 10.1 kg N ha⁻¹ yr⁻¹. Fertilizer-induced NO emission factor was estimated to be 2.4%. Total NO emission from vegetable fields in Guangdong province was roughly estimated to be 11.7 Gg N yr⁻¹ based on the vegetable field area and annual NO emission rate, and to be 13.3 Gg N yr⁻¹ based on fertilizer-induced NO emission factor and background NO emission. This means that NO emission from vegetable fields was approximately 6% of NO_x from commercial energy consumption in Guangdong province.     

Phosphorus characterization in sediments impacted by septic effluent at four sites in central Canada

Characterization of phosphorus (P) enriched solids was undertaken in the sediments below four mature septic system infiltration beds, where previous monitoring of phosphate (PO₄) concentrations in the groundwater had indicated that substantial retention of P was occurring in the vadose zone. At each site, zones of sediment P enrichment were identified by an acid extraction procedure. Acid extractable sediment P concentrations were found to be 2–5 times higher than background values, within narrow discrete zones generally 10–30 cm in thickness, located within one meter of the infiltration pipes. Back scattered electron images of the P enriched zones indicated that the P solids occurred as distinct authigenic grains (up to 300 μm diameter) and as grain coatings. Microprobe analyses indicated predominantly Fe–P in calcareous sediments (Cambridge and Langton) and Al–Fe–P in non-calcareous sediments (Muskoka and Harp Lake). Porewater analyses indicated that the zones of P accumulation were closely associated with zones of redox change characterized by the conversion of effluent NH₄⁺ to NO₃⁻. The data suggests that a substantial amount of the septic derived P is being attenuated by mineral precipitation reactions that occur rapidly after the effluent encounters subsurface sediments. Reductive dissolution of ferric (oxy)hydroxide minerals as a consequence of reducing environments near the infiltrations pipes, the release of Fe²⁺ in solution and subsequent conversion of Fe²⁺ to Fe³⁺ may promote the precipitation of ferric or ferrosoferric PO₄ minerals. In sediments with limited buffering capacity (calcite deficient), the decrease in pH resulting from effluent oxidation may cause Al (oxy)hydroxide dissolution and subsequent precipitation of Al–P rich phases. These precipitation reactions appear to have the capacity to immobilize a substantial amount of septic derived P (25–99% at these sites) for a considerable period of time.