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1.
Nonlinear isotherm behavior has been reported for the sorption of hydrophobic organic compounds (HOCs) in soil organic matter (SOM), but the exact mechanisms are unknown. Our objective was to provide insight into the sorption mechanism of HOCs in SOM by studying the sorption-desorption processes of naphthalene in a mineral soil, its humic fractions, and lignin. Additionally, humin and lignin were used for studying the effects of temperature and cosolvent on HOC sorption. All isotherms were nonlinear. The humin and lignin isotherms became more linear at elevated temperatures and with the addition of methanol indicating a condensed to expanded structural phase transition. Isotherm nonlinearity and hysteresis increased in the following order: soil humic acid (HA) < soil < soil humin. Of the samples, aliphatic-rich humin exhibited the largest degree of nonlinearity and had the highest sorption capacity for naphthalene. High nonlinearity and hysteresis in humin were most likely caused by its condensed structure. A novel aliphatic, amorphous condensed conformation is proposed. This conformation can account for both high sorption capacities and increased nonlinearity observed for aliphatic-rich samples and can explain many sorption disparities discussed in the literature. This study clearly illustrates the importance of both aliphatic and aromatic moieties for HOC sorption in SOM.  相似文献   

2.
Both natural organic matter (NOM) and surfactants are known to enhance the apparent aqueous solubility of hydrophobic organic contaminants (HOCs) in aqueous systems. In this study, the combined effect of NOM and surfactants on enhancing the solubility of HOCs was investigated, since both may occur and affect the fate and transport of HOCs in natural aqueous environments. Experimental results indicated that the apparent solubility of naphthalene, phenanthrene, and pyrene in NOM and anionic surfactant solution was lower than their solubility in NOM solution alone. However, the apparent solubility of an HOC in NOM and nonionic surfactant solution is almost the same as the sum of the HOC's solubility in NOM solution plus its solubility in nonionic surfactant solution. The observation that apparent aqueous solubility of HOCs in NOM and anionic surfactant solution is decreased is probably due to the fact that the cations that are released when the anionic surfactant dissociates may form ion pairs with acidic or phenolic groups associated with the NOM. This serves to increase the size of hydration of these groups, thereby decreasing the effective size of the nonpolar moieties associated with the NOM, and thus decreasing hydrophobic partitioning of the HOCs into the NOM. The results presented here will help us to understand the effect of NOM and surfactants on the fate and transport of HOCs in aquatic systems.  相似文献   

3.
Horseradish peroxidase- (HRP) mediated stabilization of phenolic contaminants is a topic of interest due to its potential for remediation of contaminated soils. This study evaluated the sorption of 2,4-dichlorophenol (DCP) and its HRP-mediated stabilization in two alkali-extracted soils. Alkali extraction reduced the soil organic matter (SOM) contents of the geomaterials and enriched the residual SOM with humin C. Sorption of DCP on these sorbents was complete within 1 d. However, most of the sorbed DCP was removed from the geomaterials by water and methanol, suggesting weak solute-sorbent interactions. The addition of HRP resulted in the generation of DCP polymerization products (DPP), which partitioned between the aqueous and solid phases. The DPP phase distribution was rapid and complete within 24 h. Between 70 and 90% of the added DCP was converted to DPP and up to 43% of the initial aqueous phase contaminant was transformed into a residue that was resistant to extraction with methanol. Bound residues of DPP increased with initial aqueous phase solute concentration and remained fairly constant after 7 d of contact. Contaminant stabilization was noted to be high in the humin-mineral geomaterial. Results illustrate that HRP may be effective in stabilizing phenolic contaminants in subsoils that are likely to contain SOM enriched in humin C.  相似文献   

4.
Post-treatment of leachate from soil-washing remedial actions may be necessary depending on the amounts of dissolved contaminants present. Uptake of arsenic species by surfactant-modified zeolite (SMZ) from a synthetic soil leachate (pH of approximately 12 [NaOH]) was measured as a test of SMZ as a post-treatment sorbent. Batch sorption isotherms were prepared using leachate to SMZ ratios from 40:1 to 4:1, and temperatures of 25 and 15 degrees C. Equilibrium levels of dissolved and total solution arsenic were similar. At each temperature, sorption appeared to reach a plateau or maximum, then decreased at the highest solution concentration, corresponding to the lowest amount of zeolite added (2.5 g). A maximum sorption value of 72.0 mmol of arsenic per kg of SMZ (5400 mg/kg) was observed at 25 degrees C, and 42.1 mmol/kg (3150 mg/kg) at 15 degrees C. Total arsenic recoveries varied from 74 to 125%. Surfactant-modified zeolite removed up to 97% of dissolved organic carbon and decolorized the leachate solutions. Excluding the points for the highest arsenic to SMZ ratio, the sorption isotherms were well described by the linearized form of the Langmuir equation, with coefficients of determination greater than 0.90 at both temperatures. Sorption of arsenic by SMZ is attributed to anion exchange with counterions on the surfactant head groups, and/or partitioning of organic carbon-complexed arsenic into the surfactant bilayer.  相似文献   

5.
Soil solution chemistry influences the sorption and transport behavior of hydrophobic organic compounds (HOCs) in soil. We used both batch and column studies to investigate the influence of ionic strengths (0.03 and 1.5 M) and flow velocities (12 and 24 cm h-1) on sorption and transport of naphthalene (NAP) in aggregated soil. Sorption parameters such as the Freundlich coefficient (Kf) and exponent (n) calculated from batch studies and column experiments were also compared. Retardation of NAP transport was greater at higher solution ionic strength, which may be attributed to greater sorption affinity due to enhanced aggregation of the sorbent. The effect of ionic strength on sorption of NAP observed in the batch study was consistent with the results from the column study. The Kf and n values obtained from the batch study for the two ionic strengths ranged from 7.8 to 13.7 and 0.68 to 0.80, respectively, whereas the Kf and n values obtained from the column study ranged from 7.9 to 9.9 and 0.73 to 0.85, respectively. The effluent breakthrough curve (BTC) of NAP at a flow rate of 24 cm h-1 showed significant chemical and physical nonequilibrium behavior, implying that a considerable amount of sorption in aggregated soil was time dependent when flow was relatively fast. The BTCs calculated with the parameters determined from batch studies compared poorly with the measured BTCs. The potential for nonequilibrium transport should be incorporated in models used for predicting the fate and transport of HOCs. Furthermore, caution is required when extrapolating the results from batch studies, especially for aggregated soils.  相似文献   

6.
Removal of uranium(VI) from contaminated sediments by surfactants   总被引:1,自引:0,他引:1  
Uranium(VI) sorption onto a soil collected at the Melton Branch Watershed (Oak Ridge National Laboratory, TN) is strongly influenced by the pH of the soil solution and, to a lesser extent, by the presence of calcium, suggesting specific chemical interactions between U(VI) and the soil matrix. Batch experiments designed to evaluate factors controlling desorption indicate that two anionic surfactants, AOK and T77, at concentrations ranging from 60 to 200 mM, are most suitable for U(VI) removal from acidic soils such as the Oak Ridge sediment. These surfactants are very efficient solubilizing agents at low uranium concentrations: ca. 100% U(VI) removal for [U(VI)]o,sorbed = 10(-6) mol kg-1. At greater uranium concentrations (e.g., [U(VI)]o,sorbed = ca. 10(-5) mol kg-1), the desorption efficiency of the surfactant solutions increases with an increase in surfactant concentration and reaches a plateau of 75 to 80% of the U(VI) initially sorbed. The most probable mechanisms responsible for U(VI) desorption include cation exchange in the electric double layer surrounding the micelles and, to a lesser extent, dissolution of the soil matrix. Limitations associated with the surfactant treatment include loss of surfactants onto the soil (sorption) and greater affinity between U(VI) and the soil matrix at large soil to liquid ratios. Parallel experiments with H2SO4 and carbonate-bicarbonate (CB) solutions indicate that these more conventional methods suffer from strong matrix dissolution with the acid and reduced desorption efficiency with CB due to the buffering capacity of the acidic soil.  相似文献   

7.
To evaluate the importance of both the inorganic and organic fractions in biosolids on Cd chemistry, a series of Cd sorption and desorption batch experiments (at pH 5.5) were conducted on different fractions of soils from a long-term field experimental site. The slope of the Cd sorption isotherm increased with rate of biosolids and was different for the different biosolids. Removal of organic carbon (OC) reduced the slope of the Cd sorption isotherm but did not account for the observed differences between biosolids-amended soils and a control soil, indicating that the increased adsorption associated with biosolids application was not limited to the increased OC from the addition of biosolids. Removal of both OC and Fe/Mn further reduced the slopes of Cd sorption isotherms and the sorption isotherm of the biosolids-amended soil was the same as that of the control, indicating both OC and Fe/Mn fractions added by the biosolids were important to the increased sorption observed for the biosolids-amended soil samples. Desorption experiments failed to remove from 60 to 90% of the sorbed Cd. This "apparent hysteresis" was higher for biosolids-amended soil than the control soil. Removal of both OC and Fe/Mn fractions was more effective in removing the observed differences between the biosolids-amended soil and the control than either alone. Results show that Cd added to biosolids-amended soil behaves differently than Cd added to soils without biosolids and support the hypothesis that the addition of Fe and Mn in the biosolids increased the retention of Cd in biosolids-amended soils.  相似文献   

8.
鼠李糖脂淋洗法去除土壤中重金属研究进展   总被引:6,自引:0,他引:6  
黄翔峰  杨硕  陆丽君  刘佳 《四川环境》2010,29(6):142-146
鼠李糖脂是由铜绿假单胞菌(Pseudomonas aeruginosa)产生的一种阴离子型表面活性剂,具有高效、可生物降解等特征。鼠李糖脂具有能与重金属离子络合并降低界面张力的作用,因而可以作为淋洗法的提取剂用于去除受污染土壤中的重金属。本文着重阐述了鼠李糖脂去除土壤中重金属污染的原理及影响因素。  相似文献   

9.
Clay minerals and zeolites have large cation exchange capacities, which enable them to be modified by cationic surfactant to enhance their sorption of organic and anionic contaminants. In this study, the influence of quaternary ammonium surfactants on sorption of five metal cations (Cs+, Sr+, La3+, Pb2+, and Zn2+) onto a clinoptilolite zeolite was investigated. Generally, the metal cation sorption capacity and affinity for the zeolite decreased, indicating that presorbed cationic surfactants blocked sorption sites for metal cations, as the surfactant loading on the zeolite increased. Cesium and Pb2+ sorption was affected to a small extent, indicating that selective sorption for Cs+ and specific sorption for Pb2+ play an important role in addition to cation exchange. Sorption of cationic surfactants on zeolite preloaded with different metal cations showed a strong correlation with the chain length of the surfactant tail group, while the roles of the charges and types of the metal cations were minimal. As the chain length increases, the critical micelle concentration decreases and the surfactant molecules become more hydrophobic, resulting in progressive bilayer coverage. Desorption of presorbed metal cations by cationic surfactants was strongly affected by the surfactant chain length and metal type. More metal cations, particularly Sr2+ and Zn2+, desorbed with an increase in surfactant chain length. The results, in combination with those from organic and oxyanion sorption on surfactant-modified zeolite, may be used for future surfactant modification to target sorption and desorption of a specific type of contaminant or a mixture of different types of contaminants.  相似文献   

10.
This study examines the effect of soil organic matter heterogeneity on equilibrium sorption and desorption of phenanthrene, naphthalene, 1,3,5-trichlorobenzene (1,3,5-TCB), and 1,2-dichlorobenzene (1,2-DCB) by soils and sediments. Two estuary sediments, a Pahokee peat (PP; Euic, hyperthermic Lithic Haplosaprist), and two subsamples (base- and acid-treated peat [TP] and acid-treated peat [FP]) of the peat were used as the sorbents. The contents of black carbon particles were quantified with a chemical extraction method. Petrographical examinations revealed the presence of the condensed soil and sediment organic matter (SOM) in Pahokee peat. The Freundlich isotherm model in two different forms was used to fit both sorption and desorption data. The results show that the sorption and desorption isotherms are generally nonlinear and that the apparent sorption-desorption hysteresis is present for phenanthrene and TCB. Detailed analysis of sorption data for the tested sorbent-sorbate systems indicates that black carbon is probably responsible for sorption isotherm nonlinearity for the two sediments, whereas the humic substances and kerogen may play the dominant role in nonlinear sorption by the peat. This investigation suggests that the microporosity of SOM is important for the hydrophobic organic contaminant (HOC) sorption capacity on the peat.  相似文献   

11.
Clay minerals modified with organic ions, also known as organoclays, have found applications in a wide range of organic pollution control fields because of their excellent sorption capacity towards organic pollutants. Regeneration of the spent organoclays after the sorption of organic pollutants is of great importance during their application in pollution control. In this review, the reported methods for the regeneration of the spent organoclays are summarized, including biological degradation, photo-assisted oxidation, chemical extraction/desorption, supercritical extraction, thermal desorption, et al. The characteristics and applications of these methods are briefly described. It shows that most of these methods have been developed for regenerating spent organoclays from wastewater treatment. The biological regeneration method, as an in situ, low cost and easy-operating method, is applicable for regenerating spent organoclays not only from wastewater treatment, but also from soil and groundwater remediation.  相似文献   

12.
Avermectins are widely used to treat livestock for parasite infections. Ivermectin, which belongs to the group of avermectins, is particularly hazardous to the environment, especially to crustaceans and to soil-dwelling organisms. Sorption is one of the key factors controlling transport and bioavailability. Therefore, batch studies have been conducted to characterize the sorption and desorption behavior of ivermectin in three European soils (Madrid, York, and artificial soil). The solid-water distribution coefficient (K(d)) for ivermectin sorption to the tested soils were between 57 and 396 L kg(-1) (determined at 0.1 microg g(-1)), while the organic carbon-normalized sorption coefficients (K(oc)) ranged from 4.00 x 10(3) to 2.58 x 10(4) L kg(-1). The Freundlich sorption coefficient (K(F)) was 396 (after 48 h) for the artificial soil over a concentration range of 0.1 to 50 microg g(-1), with regression constants indicating a concentration-dependent sorption. The obtained data and data in the literature are inconclusive with regard to whether hydrophobic partitioning or more specific interactions are involved in sorption of avermectins. For abamectin, hydrophobic partitioning seems to be one of the dominant types of binding, while hydrophobicity is less important for ivermectin, which is probably due to the lower lipophilicity of the molecule. Furthermore, the presence of cations such as Ca(2+) leads to decreasing sorption. Thus, it is presumed that ivermectin binds to soil by formation of complexes with immobile, inorganic soil matter. In contrast to abamectin, hysteresis could be excluded for ivermectin in the studied soils for the evaluation of sorption and desorption. The sorption mechanism is highly dependent on physicochemical properties of the avermectin.  相似文献   

13.
To investigate the potential use of anion exchange membranes (plant root simulator [PRS] probes) for isotope investigations of the soil sulfur cycle, laboratory experiments were performed to examine the sulfate exchange characteristics and to determine the extent of sulfur and oxygen isotope fractionation during sulfate sorption and desorption on the probes in aqueous solutions and simulated soil solutions. The sulfate-exchange tests in aqueous solutions under varying experimental conditions indicated that the amount of sulfate exchanged onto PRS probes increased with increasing reaction time, initial sulfate concentration, and the number of probes used (= surface area), whereas the percentage of removal of available sulfate was constant irrespective of the initial sulfate concentration. The competition of nitrate and chloride in the solution lowered the amount of exchanged sulfate. The exchange experiments in a simulated soil under water-saturated and water-unsaturated conditions showed that a considerable proportion of the soil sulfate was exchanged by the PRS probes after about 10 d. There was no evidence for significant sulfur and oxygen isotope fractionation between soil sulfate and sulfate recovered from the PRS probes. Therefore, we recommend the use of PRS probes as an efficient and easy way to collect soil water sulfate for determination of its isotope composition.  相似文献   

14.
Decisions on soil remediation are one of the most difficult management issues of municipal and state agencies. The assessment of contamination is uncertain, the costs of remediation are high, and the impacts on the environment are multiple. This paper presents a general, transparent, and consistent method for decision making among the remediation alternatives. Soil washing, phytoremediation, and no remediation are exemplarily considered. Multi-criteria utility functions including (a) the cost of remediation (b) the impact on human health and agricultural productivity, and (c) the economic gain after remediation are constructed using probability density functions representing contamination for all site coordinates. Herewith, the probability of different types of (i) correct decisions such as a hit or a true rejection and (ii) erroneous decisions such as a false alarm or miss are examined. The decision theoretic model is applied to a case study on heavy metal contaminated soil. This case study reveals the non-linear structure of multi-criteria-decision making. The case study shows that the geostatistical uncertainties of the log-normal distributed soil contamination must be taken into account: When uncertainties are not considered and the utilities are assessed according to the estimated value for a spatial unit, only few (N=26) spatial units result where the utility score of the alternative soil washing are higher than the utility score to the no remediation alternative. However, when taking into account geostatistical uncertainties of the log-normal soil distribution this number is about ten times greater (N=237). Furthermore, the use of 'maximizing expected utility' as decision rule is critical in that it may lead to a high probability of misses.  相似文献   

15.
Polymer application to soil is a growing practice to improve soil physical properties and reduce soil erosion. Polymer addition can potentially influence herbicide and pesticide sorption in soil. The one-point distribution coefficient Kd values of two herbicides in the absence and presence of each of 10 polymers (7 polyacrylamides and 3 polysaccharides) were determined by the batch equilibrium method. The results showed that nonionic napropamide [2-(alpha-naphthoxy)-N,N-diethyl propionamide] sorption was essentially unaffected by the presence of any of the polymers. The influence of polymers on anionic picloram (4-amino-3,5,6-trichloropicolinic acid) sorption depends on the charge characteristics of polymers and salt concentrations in the solution. Electrostatic interaction and competition for sorption sites are two primary underlying mechanisms for the polymer influence. At low salt concentration, the increased picloram sorption in the presence of both cationic and anionic polymers was attributed to different electrostatic interactions and polymer partitioning between soil and solution phases. At high salt levels, the presence of polymers had either no influence or a slightly negative influence on the picloram sorption, which was attributed to competition for sorption sites. In field conditions, it is more likely that polymers have no or a slightly negative influence on herbicide sorption due to the presence of salts.  相似文献   

16.
The comparison of phenol sorption on phenyltrimethylammonium (PTMA)- and benzyltrimethylammonium (BTMA)-bentonite shows a clear difference as far as phenol sorption isotherms are concerned. For PTMA-bentonite the sorption isotherm is of a straight-line character which results from simple partitioning of phenol between the aqueous and organic phases sorbed on the bentonite surface. For BTMA-bentonite the isotherm has a convex shape, characteristic of physicochemical sorption.For the first time a three-parametric model, including the dissociation constant of phenol pKa, distribution constant of phenol Kdphen and phenolate anion Kdphen between the aqueous phase and the bentonite phases is used for the evaluation of phenol sorption on organoclays with pH change. The model shows that the values of Kdphen are higher than those of Kdphen for all investigated initial phenol concentrations.The inspection of the FTIR spectrum of BTMA-bentonite loaded with phenol in the regions 1300–1600 and 1620–1680 cm−1 shows the features of π–π electron interaction between the benzene rings of phenol and the BTMA cation together with the phenol–water hydrogen bond strengthened by this interaction.  相似文献   

17.
Sorption data and subsequent predictive models for evaluating acidic pesticide behavior on variable-charge soils are needed to improve pesticide management and environmental stewardship. Previous work demonstrated that sorption of pentachlorophenol (PCP), a model organic acid, was adequately modeled by accounting for pH-and pKa-dependent chemical speciation and using two organic carbon-normalized sorption coefficients; one each for the neutral and anionic species. Such models do not account for organic anion interaction to positively charged surface sites, which can be significant for variable-charge minerals present in weathered soils typical of tropical and subtropical regions. The role of anion exchange in sorption of ionizable chemicals by variable-charge soils was assessed by measuring sorption of PCP by several variable-charge soils from aqueous solutions of CaCl2, CaSO4, Ca(H2PO4)2 as a function of pH. Differences in sorption from phosphate and chloride electrolyte solutions were attributed to pentachlorophenolate interactions with anion exchange sites. Suppression of PCP sorption by phosphate ranged from negligible in a soil with essentially no positively charge sites, as measured by negligible anion exchange capacity, to as much as 69% for variable-charge soils. Pentachlorophenolate exchange correlated well with the ratio of pH-dependent anion exchange capacity to net surface charge. Sorption reversibility of PCP by both CaCl2 and Ca(H2PO4)2 solutions was also demonstrated. Results for PCP clearly demonstrate that sorption to anion exchange sites in variable-charge soils should be considered in assessing pesticide mobility and that phosphate fertilizer application may increase the mobility of acidic pesticides.  相似文献   

18.
The use of higher plants to accelerate the remediation of petroleum contaminants in soil is limited by, among other factors, rooting depth and the delivery of nutrients to the microsites at which remediation occurs. The objective of this study was to test methods of enhancing root growth and remediation in the subsurface of a contaminated petroleum sludge. The phytoremediation of highly contaminated petroleum sludge (total petroleum hydrocarbons >35 g kg(-1) was tested in the greenhouse as a function of the frequency and the depth of irrigation and fertilization. Water and dissolved plant nutrients were added to the soil surface or at a depth of 30 cm, either daily or weekly. Equivalent quantities of water and nutrients were added in all cases. Daily irrigation at a depth of 30 cm invoked greater root growth and enhanced contaminant degradation relative to all other treatments. In the absence of plants, residual concentrations of petroleum hydrocarbons after 7 mo were higher than with plants. The presence of plant roots clearly improved the physical structure of the soil and increased microbial populations. Thus, the plant roots in conjunction with daily additions of soluble N and P appeared to enhance oxygen transport to greater depths in the soil, stimulate petroleum-degrading microorganisms, and provide microbial access to soil micropores. Subsurface irrigation with frequent, small amounts of water and nutrients could significantly accelerate phytoremediation of field soils contaminated with petroleum hydrocarbons.  相似文献   

19.
Soil water repellency in golf putting greens may induce preferential "finger flow," leading to enhanced leaching of surface applied fungicides. We examined the effects of root zone composition, treatment with a non-ionic surfactant, and the use of the fungicide iprodion or a combination of azoxystrobin and propiconazole on soil water repellency, soil water content distributions, fungicide leaching, and turf quality during 1 yr. Soil water repellency was measured using the water drop penetration time (WDPT) test and tension infiltrometers. Our study was made on a 3-yr-old experimental green seeded with creeping bentgrass (Agrostis stolonifera L.) 'Penn A-4' at Landvik in southeast Norway. The facility consists of 16 lysimeters with two different root zone materials: (i) straight sand (1% gravel, 96% sand, 3% silt and clay, 4 g kg(-1) organic matter) (SS) and (ii) straight sand mixed with garden compost to an organic matter content of 21 g kg(-1) (Green Mix [GM]). Surfactant treatment resulted in 96% lower average WDPTs at 1 cm depth, three times higher water infiltration rates at the soil surface, and reduced spatial variation in soil water contents. Fungicide leaching was close to zero for the GM lysimeters probably due to stronger sorption. Concentrations in the drainage water from SS lysimeters often exceeded surface water guideline values for all three fungicides, but surfactant treatment dramatically reduced fungicide leaching from these lysimeters. In autumn and winter, surfactant-treated plots were more infected with fungal diseases probably because of higher water content in the turfgrass thatch layer.  相似文献   

20.
Interactions of hydrophobic organic compounds (HOCs) with soil organic matter (SOM) determine their combination state in soils, and therefore strongly influence their mobility, bioavailability, and chemical reactivity. Contact time (aging) of an HOC in soil also strongly influences its combination state and environmental fate. We studied Fenton oxidation of pyrene in three different soils to reveal the influences of SOM, contact time, and combination state on the efficiency of vigorous chemical reactions. Pyrene degradation efficiency depended strongly on the dose of oxidant (H(2)O(2)) and catalyst (Fe(2+)); the greatest degradation was achieved at an oxidant to catalyst molar ratio of 10:1. Pyrene degradation differed among the three soils, ranging from 65.4% to 88.9%. Pyrene degradation efficiency decreased with increasing SOM content, and the aromatic carbon content in SOM was the key parameter. We hypothesize that pyrene molecules that combine with the compact net structure of aromatic SOM are less accessible to Fenton oxidation. Furthermore, pyrene degradation efficiency decreased considerably after aged for 30 days, but further aging to 60 and 180 days did not significantly change degradation efficiency. The Fenton oxidation efficiency of pyrene in both unaged and aged soils was greater than the corresponding desorption rate during the same period, perhaps because Fenton reaction can make pyrene more accessible to the oxidant through the enhancement of HOCs' desorption by generating reductant species or by destroying SOM through oxidation.  相似文献   

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