Benthic sediment influence on dissolved phosphorus concentrations in a headwater stream

Phosphate interacts with inorganic sediment particles through sorption reactions in streams. Collectively, this phosphorus (P) buffering mechanism can be an important determinant of soluble reactive P (SRP) concentrations. If sorption reactions control SRP concentrations in a stream, then differences in sediment characteristics may cause spatial differences in SRP concentrations. This prediction was tested by examining sediment-buffering characteristics and spatial variation in SRP among reaches with distinct sediment composition (i.e., fine versus coarse particles) in two tributaries of Boulder Creek, a headwater stream in central Wisconsin. SRP concentrations were significantly lower and algal available P and P sorption capacity were significantly higher in the reach dominated by fine sediments. Although fine particles such as sand had the greatest P sorption capacity, no retention could be attributed to biotic processes, whereas over 50% of P retention in coarse particles such as gravel could be linked to biotic uptake. Equilibrium P concentration (EPC₀) assays from different sediment fractions also indicate that biotic uptake is relatively unimportant in sand particles (EPC_live 10 μg/L: EPC_killed 10 μg/L) but very important in gravel or larger particles (EPC_live 10 μg/L: EPC_killed 80 μg/L). Thus, sediment influence on stream water P concentrations can shift predictably from abiotic sorption in reaches with fine particles to biotic retention in areas dominated by coarse sediments. Consequently, changes in sediment composition due to natural or anthropogenic disturbance have the potential to alter the type and strength of sediment-associated processes determining ambient stream P concentrations.     

Sediment‐phosphorus dynamics can shift aquatic ecology and cause downstream legacy effects after wildfire in large river systems

Global increases in the occurrence of large, severe wildfires in forested watersheds threaten drinking water supplies and aquatic ecology. Wildfire effects on water quality, particularly nutrient levels and forms, can be significant. The longevity and downstream propagation of these effects as well as the geochemical mechanisms regulating them remain largely undocumented at larger river basin scales. Here, phosphorus (P) speciation and sorption behavior of suspended sediment were examined in two river basins impacted by a severe wildfire in southern Alberta, Canada. Fine‐grained suspended sediments (<125 μm) were sampled continuously during ice‐free conditions over a two‐year period (2009–2010), 6 and 7 years after the wildfire. Suspended sediment samples were collected from upstream reference (unburned) river reaches, multiple tributaries within the burned areas, and from reaches downstream of the burned areas, in the Crowsnest and Castle River basins. Total particulate phosphorus (TPP) and particulate phosphorus forms (nonapatite inorganic P, apatite P, organic P), and the equilibrium phosphorus concentration (EPC₀) of suspended sediment were assessed. Concentrations of TPP and the EPC₀ were significantly higher downstream of wildfire‐impacted areas compared to reference (unburned) upstream river reaches. Sediments from the burned tributary inputs contained higher levels of bioavailable particulate P (NAIP) – these effects were also observed downstream at larger river basin scales. The release of bioavailable P from postfire, P‐enriched fine sediment is a key mechanism causing these effects in gravel‐bed rivers at larger basin scales. Wildfire‐associated increases in NAIP and the EPC₀ persisted 6 and 7 years after wildfire. Accordingly, this work demonstrated that fine sediment in gravel‐bed rivers is a significant, long‐term source of in‐stream bioavailable P that contributes to a legacy of wildfire impacts on downstream water quality, aquatic ecology, and drinking water treatability.     

Phosphorus sorption characteristics of sediment in the Simiyu and Kagera River basins: implications for phosphorus loading into Lake Victoria

As part of a larger study to assess the influence of land use on riverine and atmospheric phosphorus (P) loading to Lake Victoria, P sorption characteristics of eight composite bottom sediment samples from the Simiyu and Kagera rivers were determined using the Langmuir equation. The samples had low to medium Langmuir adsorption maxima (Γ_m), ranging from 107 to 201μg g^?1. Langmuir binding energy co-efficient (K) ranged from 60 to 181μg l^?1 and the equilibrium P concentration at zero sorption (EPC₀) from 0.1 to 2.75μg g^?1. By using Langmuir co-efficients derived from P sorption experiments and soluble reactive phosphorus (SRP) concentrations measured in rivers as well as the in-shore waters of Lake Victoria, it was possible to determine the potential release of SRP into the lake by sediment from the two catchments. For the 2000 water-year, it was estimated that about 28.65 ± 0.89 (mean ± SD) and 66 ± 6.76 tons of SRP were released into Lake Victoria by sediment deposited by the Simiyu and Kagera rivers, respectively. The implications of these results to future management of cultural eutrophication in Lake Victoria are also discussed.     

Vertical distribution of biological and geochemical phosphorus subcycles in two southern Appalachian forest soils

We measured Al, Fe, and P fractions by horizon in two southern Appalachian forest soil profiles, and compared solution PO₄ ^–1 removal in chloroform-sterilized and non-sterilized soils, to determine whether biological and geochemical P subcycles were vertically stratified in these soils. Because organic matter can inhibit Al and Fe oxide crystallization, we hypothesized that concentrations of non-crystalline (oxalate-extractable) Al (Al₀) and Fe (Fe₀), and concomitantly P sorption, would be greatest in near-surface mineral (A) horizons of these soils.Al₀ and Fe₀ reached maximum concentrations in forest floor and near-surface mineral horizons, declined significantly with depth in the mineral soil, and were highly correlated with P sorption capacity. Small pools of readily acid-soluble (AF-extractable) and readily-desorbable P suggested that PO₄ ^3– was tightly bound to Al and Fe hydroxide surfaces. P sorption in CHCl₃-sterilized mineral soils did not differ significantly from P sorption in non-sterilized soils, but CHCl₃ sterilization reduced P sorption 40–80% in the forest floor. CHCl₃ labile (microbial) P also reached maximum concentrations in forest floor and near-surface mineral horizons, comprising 31–35% of forest floor organic P. Combined with previous estimates of plant root distributions, data suggest that biological and geochemical P subcycles are not distinctly vertically stratified in these soils. Plant roots, soil microorganisms, and P sorbing minerals all reach maximum relative concentrations in near-surface mineral horizons, where they are likely to compete strongly for PO₄ ^3– available in solution.     

Desorption and plant-availability of phosphate sorbed by some important minerals

Experiments were conducted to study the desorption characteristics and plant-availability of phosphate sorbed by some important variable-charge minerals including kaolinite, goethite and amorphous Al oxide. Phosphate desorption from the complexes of goethite-P, kaolinite-P and Al oxide-P by equilibration with 0.02M KCl, resin or some commonly used chemical extractants was slow compared to desorption from a permanent-charge mineral (montmorillonite). However, rice plants were not observed under P deficiency in a pot trial with a phosphate-mineral complex as the only P source for both the permanent-charge mineral and the variable-charge minerals at either 50% or 100% sorption saturation with the exception of goethite-P at 50% saturation. In the exceptional goethite-P treatment, plant P concentration (1.0 g kg^–1) was on the threshold of P deficiency. From 15% to 31% of the applied P was recovered by the plants within a growing period of three months, depending on sorption saturation and mineral type. Both the dry matter yield and P uptake decreased with decreasing sorption saturation for all the tested complexes except for Al oxide-P₁₀₀ (100% saturation). In the case of Al oxide-P₁₀₀, Al toxicity may have occurred, for poor root growth and high Al concentration in the plants were observed. The effect of sorption saturation on the yield and P uptake of plant was obvious for kaolinite and goethite but not very significant for montmorillonite. Based on the recovery of applied P, the plant-availability decreased in the following order: kaolinite-P₁₀₀ > goethite-P₁₀₀ > Al oxide-P₅₀ > montmorillonite-P₁₀₀ > montmorillonite-P₅₀ > kaolinite-P₅₀ > goethite-P₅₀. Fractionation of the sorbed P before and after plant uptake showed that most of the P uptake originated from the resin-exchangeable P fraction in montmorillonite-P complex, but came mainly from NaOH-extractable fractions in goethite-P complex, whereas all the resin-P, NaHCO₃-P and NaOH-P fractions in kaolinite- and amorphous Al oxide-P complex made a contribution to P uptake.     

Al and Fe Biogeochemistry in a floodplain forest: Implications for P retention

We examined spatial and temporal variationsin soil chemistry in a floodplain forest landscape todetermine the effects of flooding on aluminum (Al) andiron (Fe) oxide biogeochemistry and inorganicphosphorus (P_i) sorption capacity. Whenpreviously sorbed P_i was considered, the sorptioncapacities of floodplain and adjacent upland soilswere comparable, suggesting that floodplain soilsrepresent a second line of defense protectingdownstream aquatic ecosystems from agriculturalrun-off. P_i sorption capacity was highlycorrelated with oxalate-extractable Al (Al_o)(r_s = 0.78); Al_o and percent organic matter(OM) were also highly correlated (r_s = 0.72),suggesting the importance of OM-Al complexes in thesesoils. The correlation of oxalate-extractable Fe(Fe_o) with OM (r_s = 0.64) was improved(r_s = 0.80) by removing lower elevation (swale)soils, suggesting that flooding inhibits theassociation of Fe_o with OM. Fe oxidecrystallinity decreased during seasonal flooding, buttotal extractable Fe did not change significantly. Fesolubilized during flooding was either replaced bysediment deposition (252 ± 3 mmol kg^–1yr^–1), and/or reprecipitated locally. Al oxidecrystallinity also decreased during flooding due to asignificant decline in NaOH-extractable Al (Al_N). Al_N concentrations subsequently returned topre-flooding levels, but sediment Al inputs (57 ±3 mmol kg^–1 yr^–1), were insufficient to account for this recovery. Observed Fetransformations suggest the importance offlooding-induced declines in soil redox potential toFe biogeochemistry; observed Al transformationssuggest the importance of complexation reactions withsoil OM to Al biogeochemistry in this floodplainforest.     

Microbially Available Phosphorus in Boreal Forests: Effects of Aluminum and Iron Accumulation in the Humus Layer

Soil microorganisms play an important role in the mobilization of phosphorus (P), and these activities may be beneficial for plant P utilization. We investigated the effects on microbial P availability of different combinations of aluminum and iron (Al + Fe) concentrations and different P pools in humus soils from boreal forest ecosystems. We measured respiration rates in laboratory incubations before and after additions of glucose plus (NH₄)₂SO₄ (Glu+N), with or without a small dose of KH₂PO₄. Glu+N was added in excess so that the availability of the inherent soil P would be growth-limiting for the microorganisms. The exponential increases observed in microbial growth after substrate additions (Glu+N) was slower for humus soils with high Al+Fe concentrations than for humus soils with low Al+Fe concentrations. Adding a small dose of KH₂PO₄ to humus soils with high Al+Fe concentrations did, however, increase the exponential growth, measured as the slope of the log-transformed respiration rates, by more than 200%. By contrast, the average increase in exponential growth was only 6% in humus soils with low Al+Fe concentrations. Almost eight times more carbon dioxide (CO₂) was evolved between the substrate additions and the point at which the respiration rate reached 1 mg CO₂ h^–1 for soils with high Al+Fe concentrations compared to humus soils with low Al+Fe concentrations. The amount of CO₂ evolved was positively related to the Al+Fe concentration of the humus soils (r ² = 0.86, P < 0.001), whereas the slope was negatively related to Al+Fe concentration (r ² = 0.70, P < 0.001). Easily available P forms were negatively related to the Al+Fe concentration, whereas organic P showed a strong positive relationship to Al+Fe (r ² = 0.85, P < 0.001), suggesting that other forms of P, as well as inorganic P, are affected by the increased sorption capacity. The results indicate that P mobilization by microorganisms is affected by the presence of sorption sites in the humus layer, and that this capacity for sorption may relate not only to phosphate but also to organic P compounds.     

Functions of Calcium-bound Phosphorus in Relation to Characteristics of Phosphorus Releasing Bacteria in Sediment of a Chinese Shallow Lake (Lake Wabu)

Sediment phosphorus (P) release accelerates lake eutrophication, while retention capacity and release potential of different P fractions, calcium-bound P (CaCO₃～P) in particular, still remains unclear. Fractionation and sorption behaviors of phosphorus were studied in sediment of a Chinese shallow lake (Lake Wabu) and two inflowing rivers from December 2011 to December 2012. Abundance of P releasing bacteria was analyzed, and their main species were isolated using a culture-dependent method and identified by their 16S rDNA sequences. CaCO₃～P release abilities of these bacteria were also tested. In sediments of both the lake and rivers studied, the rank order of the different P extracts was CaCO₃～P > iron-bound P > acid-soluble organic P > hot NaOH-extractable organic P. At the same time, CaCO₃～P content and equilibrium P concentration (EPC₀) values in river sediments were significantly higher than those in the lake. Additionally, EPC₀ changes non-monotonically with increasing CaCO₃～P content, forming a V-shaped curve, with the lowest EPC₀ at an intermediate CaCO₃～P content (around 180 mg kg^?1). Below this threshold, CaCO₃～P was a component strengthening P retention; moreover, CaCO₃～P became an active species responsible for P release. Noticeably, between the two parts divided by this threshold, the differences in abundance of inorganic phosphorus solubilizing bacteria (IPB) and organic phosphorus mineralizing bacteria (OPB) were insignificant and the dominant IPB species clustered together. By contrast, OPB was distinguished from each other, whose dominant species isolated from the part with higher CaCO₃～P content, namely Novosphingobium sp., exhibited a stronger ability to solubilize CaCO₃～P. Shortly, with lower content, CaCO₃～P tends to stabilize P in sediment; while with higher content or under eutrophic condition, it shifted into P source, with some OPB species becoming the main factors to drive its release.     

Phosphorus alleviates aluminum-induced inhibition of growth and photosynthesis in Citrus grandis seedlings

Limited data are available on the effects of phosphorus (P) and aluminum (Al) interactions on Citrus spp. growth and photosynthesis. Sour pummelo (Citrus grandis) seedlings were irrigated for 18 weeks with nutrient solution containing 50, 100, 250 and 500 μM KH₂PO₄× 0 and 1.2 mM AlCl₃· 6H₂O. Thereafter, P and Al in roots, stems and leaves, and leaf chlorophyll (Chl), CO₂ assimilation, ribulose‐1,5‐bisphosphate carboxylase/oxygenase (Rubisco) and Chl a fluorescence (OJIP) transients were measured. Under Al stress, P increased root Al, but decreased stem and leaf Al. Shoot growth is more sensitive to Al than root growth, CO₂ assimilation and OJIP transients. Al decreased CO₂ assimilation, Rubisco activity and Chl content, whereas it increased or did not affect intercellular CO₂ concentration. Al affected CO₂ assimilation more than Rubisco and Chl under 250 and 500 μM P. Al decreased root, stem and leaf P, leaf maximum quantum yield of primary photochemistry (F_v/F_m) and total performance index (PI_tot,abs), but increased leaf minimum fluorescence (F_o), relative variable fluorescence at K‐ and I‐steps. P could alleviate Al‐induced increase or decrease for all these parameters. We conclude that P alleviated Al‐induced inhibition of growth and impairment of the whole photosynthetic electron transport chain from photosystem II (PSII) donor side up to the reduction of end acceptors of photosystem I (PSI), thus preventing photosynthesis inhibition through increasing Al immobilization in roots and P level in roots and shoots. Al‐induced impairment of the whole photosynthetic electron transport chain may be associated with growth inhibition.     

Phosphorus retention in lab and field-scale subsurface-flow wetlands treating plant nursery runoff

Constructed wetland systems built to handle nutrient contaminants are often efficient at removing nitrogen, but ineffective at reducing phosphorus (P) loads. Incorporating a clay-based substrate can enhance P removal in subsurface-flow constructed wetland systems. We evaluated the potential of crushed brick, a recycled building product, and two particle sizes of a palygorskite–bentonite industrial mineral aggregate (calcined clay) to sorb P from simulated nutrient-rich plant nursery effluent. The three substrates were screened for P sorbing behavior using sorption, desorption, and equilibration experiments. We selected one substrate to evaluate in an 8-month field trial to compare field sorption capacity with laboratory sorption capacity. In the laboratory, coarse calcined clay average sorption capacity was 497 mg kg⁻¹ and it sorbed the highest percentage of P supplied (76%), except at exposure concentrations >100 mg L⁻¹ where the increased surface area of fine calcined clay augmented its P sorption capacity. Subsurface-flow mesocosms were filled with coarse calcined clay and exposed to a four and seven day hydraulic retention time treatment. Phosphorus export was reduced by 60 to 74% for both treatments until substrate P-binding sites began to saturate during month seven. During the eight month experiment, the four and seven day treatments fixed 1273 ± 22 mg kg⁻¹ P and 937 ± 16 mg kg⁻¹ P, respectively. Sequential extractions of the P saturated clay indicated that P could desorb slowly over time from various pools within the calcined clay; thus, if the calcined clay were recycled as a soil amendment, most P released would be slowly available for plant uptake and use. This study demonstrated the viability of using coarse calcined clay as a root bed substrate in subsurface-flow treatment wetlands remediating phosphorus from plant nursery runoff.     

Growth Medium and Phosphorus Supply Affect Cluster Root Formation and Citrate Exudation by Lupinus albus Grown in a Sand/Solution Split-Root System

We examined cluster root formation and root exudation by white lupin (Lupinus albus L. cv. Kiev Mutant) in response to growth medium and phosphorus supply in a sand/solution split-root system. The split-root system consisted of a nutrient solution compartment and a siliceous sand compartment. Phosphorus was applied at 1 (low-P plants) or 50 (high-P plants) μM as KH₂PO₄ to the solution compartment and at 10, 50 or 250 mg P kg⁻¹ as hydroxyapatite (Ca-P) to the sand compartment. In contrast to the high-P plants, P concentration and P uptake in the low-P plants increased with increasing P supply to the sand compartment. The NaHCO₃-extractable P was lower in the rhizosphere of the low-P plants than the high-P ones. The proton extrusion rate by the solution-grown roots of the low-P plants was higher than that of the high-P plants at the early growth stage. For the low-P plants, the proportion of dry root biomass allocated to cluster roots was higher in the solution compartment than that in the sand compartment. The citrate exudation increased in the sand compartment and decreased in the solution compartment with time, showing a lack of synchronization in citrate exudation by two root halves grown in different media. The cluster root proportion and citrate exudation in both compartments decreased with increasing shoot P concentration. An additional experiment with no P added to either root compartment showed that the proportion of cluster roots was about 9% lower in the sand than solution compartments. The results suggest that cluster root formation and citrate exudation can be significantly affected by the root growth medium in addition to being regulated by shoot P status. More P can be exploited from sparingly available Ca-P by the low-P plants than the high-P ones due to greater citrate exudation under P deficiency.     

Use of blast furnace granulated slag as a substrate in vertical flow reed beds: field application

Research was conducted at Middle East Technical University (METU), Ankara, Turkey in 2000 to determine whether a reed bed filled with an economical Turkish fill media that has high phosphorus (P) sorption capacity, could be implemented and operated successfully under field conditions. In batch-scale P-sorption experiments, the P-sorption capacity of the blast furnace granulated slag (BFGS) of KARDEMIR Iron and Steel Ltd., Co., Turkey, was found to be higher compared to other candidate filter materials due to its higher Ca content and porous structure. In this regard, a vertical subsurface flow constructed wetland (CW) (30 m(2)), planted with Phragmites australis was implemented at METU to treat primarily treated domestic wastewater, at a hydraulic rate of 100 mm d(-1), intermittently. The layers of the filtration media constituted of sand, BFGS, and gravel. According to the first year monitoring study, average influent and effluent total phosphorus (TP) concentrations were 6.61+/-1.78 mg L(-1) and 3.18+/-1.82 mg L(-1); respectively. After 12 months, slag samples were taken from the reed bed and P-extraction experiments were performed to elucidate the dominant P-retention mechanisms. Main pools for P-retention were the loosely-bounded and Ca-bounded P due to the material's basic conditions (average pH>7.7) and higher Ca content. This study indicated the potential use of the slag reed bed with higher P-removal capacity for secondary and tertiary treatment under the field conditions. However, the P-sorption isotherms obtained under the laboratory conditions could not be used favorably to determine the longevity of the reed bed in terms of P-retention.     

The effect of aluminium and media on the growth of mycorrhizal and nonmycorrhizal highbush blueberry plantlets

A factorial experiment was conducted to determine the effect of aluminium (0 and 600M) and media (sand, and 1:1 sand:soil) on mycorrhizal (M) and non-mycorrhizal (NM) highbush blueberry plantlets. There were no differences in nutrient uptake and total plant dry weight between M and NM plantlets. However, more root growth, as determined by dry weight, was observed in M than NM plantlets. The plantlets growing in sand had more dry weight than did those in the soil medium. Although the root growth and shoot growth were reduced by the 600M Al treatment, the direct effect of Al on plantlet growth was not clear due to Al and P interactions. Plant nutrient uptake was reduced by high concentrations of Al, suggesting that high Al concentration limited the ability of roots to acquire most of the nutrients. Mycorrhizal cortical cell infection levels of 15–20% wene maintained in the roots in soil medium but decreased to about 5% over the 6 weeks of the experiment in the sand medium. Although M plantlets accumulated more Al in their roots, Al was readily transported to the leaf tissues of M and NM plantlets.     

Al avoidance and Al tolerance ofMucuna pruriens var.utilis: Effects of a heterogeneous root environment and the nitrogen form in the root environment

InMucuna pruriens var.utilis, grown with nitrate-N in a hydroponic split-root system, an Al avoidance reaction of root growth was observed, which was ascribed to local P stress in the Al containing compartment. The Al avoidance reaction was similar to the avoidance ofMucuna roots of acid subsoil in the field where roots grew preferentially in the topsoil. In the present paper the effect of different N forms (NO₃ ^– and NH₄ ⁺) on the reactions ofMucuna to Al were studied, since in acid soils N is present as a mixture of NO₃ ^– and NH₄ ⁺. No interaction between the N form and Al toxicity was found. A hydroponic split-root experiment with NH₄NO₃ nutrition, which is comparable to the situation in the field, showed that under these conditions Al avoidance did not occur. It is concluded that a relation between the Al avoidance reaction ofMucuna and P stress is still likely.Abbreviations D_r root diameter - L_pr total root length per plant - L_rw specific root length - NRA nitrate reductase activity - S/R shoot: root ratio     

Effects of aluminium on growth and root reactions of phosphorus stressed Betula pendula seedlings

The impact of two constant non-toxic levels of Al stress (0.2 and 0.4 mM) on growth and ³²P uptake capacity on sub-optimal (P-limited) Betula pendula seedlings grown in sand culture was examined.Seedling growth was under optimum controlled conditions in a growth chamber where nutrient additions were made at a predetermined relative addition rate (R_A) of 10% day^-1. Three treatment groups of seedlings 0, 0.2 and 0.4 mM Al were harvested at 15, 29 and 42 days. The excised roots were exposed to a ³²P-labelled solution for 15 minutes to measure their capacity for P uptake. Growth was determined by weighing the roots, stems and leaves of the seedlings.Growth data showed that relative growth rate (R_G) should equal the R_A of P the most limiting nutrient, which was supplied at P/N 3% instead of an optimal 15%. Therefore, Ingestad's theory can also be used succesfully in sand culture and this may be particularly important for future studies of root and rhizosphere exudates. Low levels of Al (< 0.2 mM) in combination with low P supply significantly lowered the R_G of the birch seedlings by further reducing P supply. However, previous studies of birch seedling growth and nutrient uptake using Ingestad's solution culture technique with optimumal P supply did not show any effect of Al on growth untill the Al was in excess of 3 mM. Aluminium was not directly toxic to the plants and therefore roots could respond to the ³²P bioassay.     

Organic chemistry of Protosalvinia (Foerstia) from the Chattanooga and New Albany Shales

Vertical samplings of Protosalvinia, a thalloid Upper Devonian alga from the Chattanooga and New Albany Shales, are chemically analyzed and correlated with the organic chemical constituents isolated from associated shale matrices. Normal, saturated acids (n-C₈ to n-C₃₆n-paraffins (C₁₀ to C₃₆), showing an odd carbon-number preference, branched-chain alkanes, and vanadyl porphyrins isolated from Protosalvinia vary in their concentrations with depth of burial and with the dominant associated morphology of Protosalvinia, i.e., P. arnoldii, P. ravenna, P. furcata. Organic constituents of shales, in general, reflect those detected in thalli; relative concentrations, molecular diversity, carbon chain-lengths and maxima of compounds extracted from both shale and fossil material are similar. Pristane, phytane and porphyrins are probably derived from a chlorophyllous organism, while δ¹³C data corroborate a photosynthetic system operating in the primary biosynthesis of shale geochemistry. Crude-oil extracts of Protosalvinia-rich strata contain higher alkane and lower aromatic hydrocarbon concentrations than those of an average crude oil. Chemical variations among forms of Protosalvinia suggest biochemical differences in original plant composition rather than diagenetic transitions; field observations of morphological trends seen in vertical samplings may be used in crude extrapolations of the organic chemical compositions of shale strata.     

Stabilization of Soil Organic Matter: Association with Minerals or Chemical Recalcitrance?

Soil organic matter (OM) can be stabilized against decomposition by association with minerals, by its inherent recalcitrance and by occlusion in aggregates. However, the relative contribution of these factors to OM stabilization is yet unknown. We analyzed pool size and isotopic composition (¹⁴C, ¹³C) of mineral-protected and recalcitrant OM in 12 subsurface horizons from 10 acidic forest soils. The results were related to properties of the mineral phase and to OM composition as revealed by CPMAS ¹³C-NMR and CuO oxidation. Stable OM was defined as that material which survived treatment of soils with 6 wt% sodium hypochlorite (NaOCl). Mineral-protected OM was extracted by subsequent dissolution of minerals by 10% hydrofluoric acid (HF). Organic matter resistant against NaOCl and insoluble in HF was considered as recalcitrant OM. Hypochlorite removed primarily ¹⁴C-modern OM. Of the stable organic carbon (OC), amounting to 2.4–20.6 g kg⁻¹ soil, mineral dissolution released on average 73%. Poorly crystalline Fe and Al phases (Fe_o, Al_o) and crystalline Fe oxides (Fe_d−o) explained 86% of the variability of mineral-protected OC. Atomic C_p/(Fe+Al)_p ratios of 1.3–6.5 suggest that a portion of stable OM was associated with polymeric Fe and Al species. Recalcitrant OC (0.4–6.5 g kg⁻¹ soil) contributed on average 27% to stable OC and the amount was not correlated with any mineralogical property. Recalcitrant OC had lower Δ¹⁴C and δ¹³C values than mineral-protected OC and was mainly composed of aliphatic (56%) and O-alkyl (13%) C moieties. Lignin phenols were only present in small amounts in either mineral-protected or recalcitrant OM (mean 4.3 and 0.2 g kg⁻¹ OC). The results confirm that stabilization of OM by interaction with poorly crystalline minerals and polymeric metal species is the most important mechanism for preservation of OM in these acid subsoil horizons.     

Phosphorus retention capacity of agricultural headwater ditch sediments under alkaline condition in purple soils area,China

Phosphorus (P) retention by headwater ditch sediments adsorption plays a pivotal ecological role in P buffering in freshwater ecosystems. Previous studies focused on headwater ditch sediment adsorption and its P retention capacity in acid conditions, but little information is available for headwater ditches under alkaline condition. In this study, adsorption behavior of phosphorus was investigated in headwater ditch sediments under alkaline condition using a batch equilibrium technique, thus determining phosphorus retention capacity of headwater ditch sediments collected at 11 sites at base-flow on 2 March 2006 in purple soils area of China. Results showed that headwater ditch sediments had elevated phosphorus sorption maximum (S_max) values (122.72–293.23 mg P kg^?1) and P binding energy (K) values (1.64–8.65 L mg^?1), while they had low equilibrium phosphorus concentration (EPC₀) (0.001–0.108 mg L^?1) and degree of phosphorus saturation (DSP) (1.93–10.19%). Analysis of EPC₀ and soluble P concentration indicated that sediments acted as a sink for P across all headwater ditches. Therefore, there were high intrinsic P retention capacities of headwater ditch sediments. Positive correlations of both K and S_max with oxalate-extractable Fe (r of 0.93 and 0.81, p < 0.05) and total carbon (TC) (r of 0.89 and 0.74, p < 0.05) were found, thus suggesting that organic matter and amorphous or poorly crystalline Fe would play dominant roles in P adsorption in the headwater ditch sediments under alkaline condition. Since neither S_max nor K were correlated with CCE (CaCO₃) (r of 0.15 and ?0.06, p > 0.05), the high-energy sorptive surfaces of Fe oxides were more important than CaCO₃ in P sorption of sediment under alkaline condition. At the same time, these poor correlations between CCE and K and S_max imply a non-linear relationship between P retention and the content of carbonate. The negative correlations of both K and S_max with pH (r of–0.73, and–0.58, p < 0.05) revealed that an increase in pH would not improve sediment retention capacity under alkaline conditions.     

Phosphorus saturation and pH differentially regulate the efficiency of organic acid anion-mediated P solubilization mechanisms in soil

Exudation of organic acid anions by plants as well as root-induced changes in rhizosphere pH can potentially improve phosphate (P_i) availability in the rhizosphere and are frequently found to occur simultaneously. In non-calcareous soils, a major proportion of P_i is strongly sorbed to metal oxi(hydr)oxides of mainly iron (Fe) and aluminium (Al) and organic anions are known to compete with P_i for the same sorption sites (ligand exchange) or solubilize P_i via ligand-promoted mineral dissolution. Root-induced co-acidification may also further promote P_i release from soil. The relative efficiency of these different solubilization mechanisms, however, is poorly understood. The aims of this study were to gain a better mechanistic understanding of the solubilizing mechanisms of four carboxylates (citrate, malate, oxalate, malonate) in five soils with high and low P surface site saturation. Results indicate that at a lower P saturation of solid phase sorption sites, ligand-promoted mineral dissolution was the main P_i solubilization mechanism, while ligand exchange became more important at higher soil P concentrations. Co-acidification generally increased P_i solubility in the presence of carboxylates; however the relative solubilizing effect of carboxylates compared to the background electrolyte (KCl) control decreased by 20–50%. In soils with high amounts of exchangeable calcium (Ca), the proton-induced Ca solubilization reduced soluble P_i, presumably due to ionic-strength-driven changes in the electric surface potential favoring a higher P_i retention. Across a wider soil pH range (pH 3–8), P_i solubility increased with increasing alkalinity, as a result of both, more negatively charged sorption sites, as well as DOC-driven changes in Fe and Al solubility, which were further enhanced by the presence of citrate. Overall, the relative efficiency of carboxylates in solubilizing P_i was greatest in soils with medium to high amounts of anionic binding sites (mainly Fe- and Al-oxy(hydr)oxides) and a medium P sorption site coverage, with citrate being most effective in solubilizing P_i.     

Nitrogen removal from secondary effluent by using integrated constructed wetland system

The treatment capacity of an integrated constructed wetland system (CWS) that was designed to reduce nitrogen (N) from secondary effluent was explored. The integrated CWS consisted of vertical-flow constructed wetland, floating bed and sand filter. The vertical-flow wetland was filled with gravel, steel slag and peat from the bottom to the top. Vetiver zizanioides was selected to grow in the vertical-flow constructed wetland and Coix lacrymajobi L. was grown in the floating bed. The results showed that the integrated CWS displayed superior removal efficiency for nitrate nitrogen (NO₃⁻-N), ammonia nitrogen (NH₄⁺-N), nitrite nitrogen (NO₂⁻-N), and total nitrogen (TN). The average NO₃⁻-N, NO₂⁻-N, NH₄⁺-N and TN removal efficiencies of the integrated CWS were 98.83%, 95.60%, 98.05% and 92.41%, respectively, during the whole experimental operation. The integrated CWS may have a good potential for removing N from secondary effluent.