Effect of common ions aging treatment on adsorption of phosphate onto and control of phosphorus release from sediment by lanthanum-modified bentonite.

The objective of this work was to explore the influence of combined aging treatment using Na+, Ca2+, Cl-, HCO3- and SO42- on the adsorption of phosphate (HiPO4i-3) onto and the restraint of internal phosphorus (P) migration into overlying water (OW) by lanthanum modified bentonite (LMB). To achieve this aim, the adsorption characteristics and mechanisms of HiPO4i-3 onto the raw and aged LMBs (named as R-LMB and A-LMB, respectively) were comparatively studied, and the effects of R-LMB and A-LMB treatments (addition and capping) on the migration of P from sediment to OW were comparatively investigated. The results showed that the combined aging treatment of R-LMB with Na+, Ca2+, Cl-, HCO3- and SO42- inhibited the adsorption of HiPO4i-3. Similar to R-LMB, the precipitation of HiPO4i-3 with La3+ to form LaPO4 and the ligand exchange between CO32- and HiPO4i-3 to form the inner-sphere lanthanum-phosphate complexes are the important mechanisms for the HiPO4i-3 uptake by A-LMB. The R-LMB addition and capping can be effective in the suppression of endogenous P release to OW under hypoxia conditions. The inactivation of diffusive gradient in thin film-unstable P (DGT-UP) and potentially mobile P (PM-P) in sediment acted as a key role in the restraint of internal P release to OW by the R-LMB addition, and the immobilization of DGT-UP and PM-P in the topmost sediment played a key role in the interception of endogenous P migration into OW by the R-LMB capping. Although the Na+/Ca2+/Cl-/HCO3-/SO42- combined aging treatment had a certain negative effect on the efficiencies of LMB addition and capping to hinder the liberation of P from sediment into OW, the A-LMB addition and capping still can be effective in the control of sediment internal phosphorus pollution to a certain degree. The results of this work indicate that LMB has a high potential to be used as a capping/amendment material to control internal phosphorus pollution.

Effectiveness and mechanism of aluminum/iron co-modified calcite capping and amendment for controlling phosphorus release from sediments.

The effectiveness and mechanism of aluminum/iron co-modified calcite (Al/Fe-CA) for the control of phosphorus (P) liberation from sediments was investigated. The results showed that Al/Fe-CA possessed good sorption performance for phosphate, and the maximum phosphate sorption capacity for Al/Fe-CA could reach 27.0 mg/g. The major mechanisms involved the surface adsorption of phosphate on calcite, the precipitation between phosphate and Ca2+ leached from calcite, and the ligand exchange between Al/Fe-bound hydroxyl groups and phosphate to form the Al-O-P and Fe-O-P inner-sphere complexes. The re-releasing risk of Al/Fe-CA-bound P under the circumstances of normal pH (5-9) and reducing environment was very low. Al/Fe-CA addition could significantly reduce the risk of P releasing from sediment to overlying water (OL-water), and the inactivation of mobile P, reactive soluble P (SRP) and diffusive gradient in thin-films (DGT)-labile P in sediment by Al/Fe-CA had a great part in the suppression of sediment-P liberation to OL-water by the Al/Fe-CA amendment. Al/Fe-CA capping and fabric-wrapped Al/Fe-CA capping both could greatly reduce the risk of P releasing from sediment into OL-water, and the formation of a static layer with low concentrations of SRP and DGT-labile P in the upper sediment was the key to sustaining a high P controlling efficiency. When the applied mode of Al/Fe-CA varied from capping to amendment, although the inactivation efficiency of DGT-labile P in the overlying water and upper sediment by Al/Fe-CA would decrease to a certain degree, the inactivation efficiency of DGT-labile P in the lower sediment by Al/Fe-CA would increase. Results of this study suggest that Al/Fe-CA has the high potential to be used as an active capping or amendment material for the management of internal P loading in surface water bodies.

Magnetite-modified activated carbon based capping and mixing technology for sedimentary phosphorus release control.

In this study, magnetite-modified activated carbon (MAC) was synthesized, characterized and used as capping and amendment materials to control sedimentary phosphorus (P) release. Batch experiments were applied to determine the behavior of phosphate adsorption and desorption on/from MAC. Sediment incubation experiments were utilized to evaluate the impact of MAC capping and addition on the mobilization of P in sediments. Sediment capping and amendment with MAC both can greatly reduce the amount of reactive soluble P (RS-P) in the overlying water (OLY-water), with a reduction efficiency of higher than 83%. MAC capping and amendment both can significantly reduce the concentrations of labile P measured by diffusive gradient in thin-films (DGT) in the upper sediment, which gives rise to in the formation of the static layer of P (P-S-Layer) in the upper sediment. The forms of P bound by MAC were mainly redox-sensitive P (PRS), NaOH extractable inorganic P (IPNaOH) and HCl extractable P (PHCl), which accounted for 47.2, 18.5 and 32.9% of the total adsorbed P, respectively. Almost half of P adsorbed by MAC existed in the form of PRS, which is easy to be released under anoxic condition, and the retrieval of MAC from the waterbody after its application is very necessary. The concentrations of RS-P in OLY-water and mean DGT-labile P in P-S-Layer under capping condition were much less than those under amendment condition. The reduction of the apparent diffusion efflux of P across the interface between OLY-water and sediment by the MAC capping was much larger than that by the MAC amendment. Results of this work suggest that MAC capping and amendment are very promising methods for blocking the liberation of P from sediments into OLY-water, and MAC capping can achieve a higher efficiency of sedimentary P release control compared to MAC amendment.

Simultaneous control of nitrogen and phosphorus release from sediments using iron-modified zeolite as capping and amendment materials.

The use of zeolite as a geo-engineering tool has a high potential to control nitrogen (N) release from sediments, but its efficiency for controlling sedimentary phosphorus (P) release still need to be further increased. To address this issue, this work synthesized an iron-modified zeolite (IM-Z) by coating iron onto the surface of natural zeolite (NAT-Z) and then the as-obtained IM-Z was utilized as a geo-engineering material to block the upward mobilization of N and P from sediments to the overlying water. The efficiencies of IM-Z covering and amendment to prevent the liberation of N and P from sediments were evaluated, and the controlling mechanism was explored. Capping and amendment with IM-Z not only resulted in the tremendous reduction of the levels of ammonium-N (NH4+-N) and reactive soluble P (RSP) in the overlying water, but also led to the decrease of the contents of NH4+-N and RSP in the pore water. More importantly, sediment capping and amendment with IM-Z resulted in the formation of a static layer in the upper sediment directly below the sediment-water interface, with very low concentration of RSP in the pore water. In addition, IM-Z capping and addition effectively immobilized the diffusive gradients in thin films (DGT)-labile P in the overlying water and sediment. Furthermore, the decrease of the DGT-labile Fe concentrations in the overlying water as well as the top sediment were also observed after IM-Z capping and addition. Nearly 70% of P bound by IM-Z is stable and difficult to be released back into the overlying water under common pH and anoxic conditions. The adsorption of pore water NH4+-N on IM-Z, the immobilization of pore water RSP and DGT-labile P by IM-Z and the uptake of DGT-labile Fe on IM-Z played a significant role in the simultaneous control of NH4+-N and RSP liberation. Compared to NAT-Z, the efficiency of IM-Z to block the liberation of sedimentary P was higher. Results of this study demonstrate that IM-Z is suitable for use in the simultaneous interception of the upward transportation of NH4+-N and RSP from sediments into the overlying water.

Effect of precipitation pH and coexisting magnesium ion on phosphate adsorption onto hydrous zirconium oxide.

To understand the effect of precipitation pH and coexisting Mg2+ on phosphate adsorption onto zirconium oxide (ZrO2), ZrO2 particles precipitated at pH 5.3, 7.1 and 10.5, i.e., ZrO2(5.3), ZrO2(7.1) and ZrO2(10.5), respectively were prepared and characterized, then their adsorption performance and mechanism in the absence and presence of Mg2+ were comparatively investigated in this study. The results showed that the Elovich, pseudo-second-order and Langmuir isotherm models correlated with the experimental data well. The adsorption mechanism involved the complexation between phosphate and zirconium. Coexisting Mg2+ slightly inhibited the adsorption of phosphate on ZrO2(5.3), including the adsorption capacity and rate, but coexisting Mg2+ greatly increased the adsorption capacity and rate for ZrO2(7.1) and ZrO2(10.5). The enhanced adsorption of phosphate on ZrO2(7.1) and ZrO2(10.5) in the presence of Mg2+ was mainly due to the formation of Mg2+-HPO42- ion pair (MgHPO40) in the solution and then the adsorption of MgHPO40 on the adsorbent surface, forming the phosphate-bridged ternary complex Zr(OPO3H)Mg. In the absence of Mg2+, the maximum phosphate adsorption capacity at pH 7 calculated from the Langmuir isotherm model decreased in the order of ZrO2(7.1) (67.3 mg/g) > ZrO2(5.3) (53.6 mg/g) ≈ ZrO2(10.5) (53.1 mg/g), but it followed the order of ZrO2(7.1) (97.0 mg/g) > ZrO2(10.5) (79.7 mg/g) > ZrO2(5.3) (51.3 mg/g) in the presence of Mg2+. The results of this work suggest that ZrO2(7.1) is more suitable for use as an adsorbent for the effective removal of phosphate from municipal wastewater than ZrO2(5.3) and ZrO2(10.5), because Mg2+ is generally present in this wastewater.

Effect of pre-treatment of bentonite with sodium and calcium ions on phosphate adsorption onto zirconium-modified bentonite.

To understand the influence of the pre-treatment of bentonite with Na+ and Ca2+ on the adsorption of phosphate on zirconium-modified bentonite, three kinds of adsorbent materials including zirconium-modified raw, Na+-pretreated and Ca2+-pretreated bentonites were synthesized and characterized firstly, and afterward their adsorption performance and mechanism for phosphate were studied comparatively. The phosphate adsorption ability for zirconium-modified bentonite decreased after the pre-treatment of bentonite with Na+, but it increased after the pre-treatment of bentonite with Ca2+. The maximum phosphate adsorption capacity calculated from the Langmuir isotherm model for zirconium-modified Ca2+-pretreated bentonites (13.4 mg P/g) was much higher than that for the zirconium-modified raw bentonite (9.06 mg P/g). The pre-treatment of bentonite with Na+ and Ca2+ did not change the interaction type between zirconium-modified bentonite and phosphate, i.e., the coordination of phosphate to zirconium. The decreased phosphate adsorption capacity for zirconium-modified bentonite induced by the Na+ pre-treatment could be mainly attributed to the decrease of the specific surface area and the content of exchangeable Ca. The increased phosphate adsorption capacity for zirconium-modified bentonite induced by the Ca2+ pre-treatment could be mainly due to the increase in the amount of exchangeable Ca. Results of this work suggest that the zirconium-modified Ca2+-pretreated bentonite is more suitably used as an adsorbent for the removal of phosphate from wastewater than the zirconium-modified raw and Na+-pretreated bentonites.

Identification of weak transitions using moving-window two-dimensional correlation analysis: treatment with scaling techniques.

In the present study, the theory of the data treatment with scaling techniques for moving-window two-dimensional (scaling-MW2D) correlation analysis was first proposed. This new analytical method of spectroscopy can significantly enhance the resolving capacity of the moving-window two-dimensional (MW2D) correlation infrared spectroscopy in the direction of the perturbation variable. So, it strengthened the ability of MW2D to highlight the weak transitions. The in situ infrared spectra of four common polymers, including polyamide 66 (PA66), polystyrene-block-polybutadiene-block-polystyrene block copolymer (SBS), isotactic polypropylene (iPP), and polyoxymethylene (POM), were employed to illustrate the advantages of scaling-MW2D. In the applications of the present study, the conventional autocorrelation MW2D can only distinguish the melting point of PA66, the maximum crystallization temperature of POM, and the primary oxidation of SBS. However, the autocorrelation scaling-MW2D not only can more easily determine the above transitions, but also can identify PA66 brill transition, the dissociation of adsorbed water in PA66, POM secondary crystallization, the glass transition of hard blocks in SBS, and the generation of the aldehyde and hydroxyl groups during SBS oxidation. Our further study found that the selection of the scaling factor α was very important. The golden point α = 0.618 was the best value, and satisfactory application results can be achieved. The slice scaling-MW2D was also investigated. The scaling-MW2D method of spectroscopy can be used elsewhere. The application of this analytical method should not be limited to the infrared spectra, and it also should not be limited to transitions in polymers. This method can be easily extended and applied to other materials and spectra.

Control of phosphorus release from sediment by iron/aluminum co-modified zeolite: efficiency, mechanism, and response of microbial communities in sediment.

The efficiency of iron/aluminum co-modified zeolite (FeAl-Z) covering and amendment for controlling the internal loading of phosphorus (P) from sediment to the overlying water (OW) and its controlling mechanism were explored. The response of the composition of sedimentary microbial communities in sediment and their function to the FeAl-Z capping and amendment was also examined. FeAl-Z showed good removal performance for phosphate in aqueous solution. The maximum phosphate adsorption quantity for FeAl-Z at pH 7 attained 11.2 mg P/g. The release of sediment endogenous phosphorus to OW can be successfully restrained by the FeAl-Z covering and amendment, and the suppression ability of FeAl-Z covering was stronger than that of FeAl-Z amendment. Under the capping or amendment condition, FeAl-Z can effectively inactivate the labile phosphorus measured by diffusion gradient in thin film (DGT-LP) in the overlying water and surface sediment. The added FeAl-Z transformed redox-sensitive phosphorus (BD-P) to metal oxide-bound phosphorus (NaOH-IP) and residual phosphorus (Res-P) in sediment, which increased the stability of inorganic phosphorus in the sediment. The passivation of soluble reactive phosphorus (SRP) and DGT-LP in the surface sediment by FeAl-Z significantly contributed to the inhibition of sediment endogenous phosphorus release to OW by the FeAl-Z capping, and the passivation of SRP, DGT-LP and mobile phosphorus in the surface sediment played a pivotal role in the control of sediment internal phosphorus release by the FeAl-Z amendment. The FeAl-Z amendment and capping did not increase the liberation risk of Fe from sediment, and the microorganisms in the sediments under the conditions of FeAl-Z amendment and covering still can perform good ecological functions. Results of this research demonstrate that FeAl-Z capping has high application potential in the control of phosphorus transfer from sediment to OW.

Effect of capping mode on control of phosphorus release from sediment by lanthanum hydroxide.

The use of in situ active capping to control phosphorus release from sediment has attracted more and more attentions in recent years. It is important to identify the effect of capping mode on the control of phosphorus release from sediment by the in situ active capping method. In this study, the impact of capping mode on the restraint of phosphorus migration from sediment into overlying water (OW) by lanthanum hydroxide (LH) was studied. Under no suspended particulate matter (SPM) deposition condition, LH capping effectively restrained the liberation of endogenous phosphorus into OW during anoxia, and the inactivation of diffusive gradient in thin film-unstable phosphorus (UPDGT) and mobile phosphorus (PMobile) in the topmost sediment served as a significant role in the restraint of endogenous phosphorus migration into OW by LH capping. Under no SPM deposition, although the transformation of capping mode from the single high dose capping to the multiple smaller doses capping had a certain negative impact on the restraint efficiency of endogenous phosphorus liberation to OW by LH in the early period of application, it increased the stability of phosphorus in the static layer in the later period of application. Under SPM deposition condition, LH capping had the capability to mitigate the risk of endogenous phosphorus liberation into OW under anoxia conditions, and the inactivation of UPDGT and PMobile in the topmost sediment was a significant mechanism for the control of sediment phosphorus liberation into OW by LH capping. Under SPM deposition condition, the change in the covering mode from the one-time high dose covering to the multiple smaller doses covering decreased the efficiency of LH to limit the endogenous phosphorus transport into OW in the early period of application, but it increased the performance of LH to restrain the sedimentary P liberation during the later period of application. The results of this work suggest that the multiple LH capping is a promising approach for controlling the internal phosphorus loading in freshwater bodies where SPM deposition often occurs in the long run.

Comparison of magnetite, hematite and goethite amendment and capping in control of phosphorus release from sediment.

The characteristics and mechanism of phosphate adsorption onto magnetite, hematite and goethite were comparatively studied, and the effects of magnetite, hematite and goethite amendment and capping on endogenous phosphorus (P) liberation from sediment into overlying water (OW) were comparatively investigated. The adsorption of phosphate onto magnetite, hematite and goethite mainly obeyed the inner-sphere complexation mechanism, and the phosphate adsorption capacity decreased in the order of magnetite > goethite > hematite. The magnetite, hematite and goethite amendment all can decrease the risk of endogenous Prelease into OW under anoxic conditions, and the inactivation of diffusion gradients in thin films-labile P in sediment made a great contribution to the restraint of endogenous P release into OW by the magnetite, hematite and goethite amendment. The efficiency of endogenous P release restraint by the iron oxide addition decreased in the order of magnetite > goethite > hematite. The magnetite, hematite and goethite capping all can be effective for the suppression of endogenous P release from sediment into OW under anoxic conditions, and most of P immobilized by the magnetite, hematite and goethite capping layers is relatively or very stable. The results obtained from this work suggest that magnetite is more suitably used a capping/amendment material to prevent P release from sediment than hematite and goethite, and magnetite capping is a promising approach for hindering sedimentary P release into OW.

Immobilization of phosphorus in water-sediment system by iron-modified attapulgite, calcite, bentonite and dolomite under feed input condition: Efficiency, mechanism, application mode effect and response of microbial communities and iron mobilization.

Four kinds of iron-based materials, i.e., iron-modified attapulgite, calcite, bentonite and dolomite (abbreviated as Fe-ATP, Fe-CA, Fe-BT and Fe-DOL, respectively) were prepared and used to immobilize the phosphorus in the system of overlying water (O-water) and sediment under the feed input condition, and their immobilization efficiencies and mechanisms were investigated. The influence of application mode on the immobilization of phosphorus in the water-sediment system by Fe-ATP, Fe-CA, Fe-BT and Fe-DOL was researched. The effects of Fe-ATP, Fe-CA, Fe-BT and Fe-DOL on the concentration of labile iron in the water-sediment system and the microbial communities in sediment were also studied. The results showed that the Fe-ATP, Fe-CA, Fe-BT and Fe-DOL addition all can effectively immobilize the soluble reactive phosphorus (SRP), dissolved total phosphorus (DTP) and diffusive gradients in thin-films (DGT)-labile phosphorus in O-water under the feed input condition, and also had the ability to inactivate the DGT-labile phosphorus in the top sediment. Although the change in the application mode from the one-time addition to the multiple addition reduced the inactivation efficiencies of SRP and DTP in O-water in the early period of application, it increased the immobilization efficiencies in the later period of application. Although Fe-ATP, Fe-CA, Fe-BT and Fe-DOL had a certain releasing risk of iron into the pore water, they had negligible risk of iron release into O-water. The addition of Fe-ATP, Fe-CA, Fe-BT or Fe-DOL reshaped the sediment bacterial community structure and can affect the microorganism-driven phosphorus cycle in the sediment. Results of this work suggest that Fe-ATP, Fe-CA, Fe-BT and Fe-DOL are promising phosphorus-inactivation materials to immobilize the phosphorus in the water-sediment system under the feed input condition.

Control of phosphorus release from sediment by hydrous zirconium oxide combined with calcite, bentonite and zeolite.

This study investigated the effectiveness and mechanism for the control of internal phosphorus (P) liberation from sediment by hydrous zirconium oxide (HZrO2) combined with calcite, bentonite and zeolite. The results suggested that coexisting calcite, calcium-modified bentonite (CaBT) and calcium-modified zeolite (CaZ) all had the ability to promote the adsorption of phosphate (PO43-) onto HZrO2. The mechanisms of PO43- elimination by HZrO2/calcite mixture involved the adsorption of PO43- on calcite, the precipitation of PO43- with Ca2+, and the inner-sphere complexation of PO43- with HZrO2. The amendment of sediment with HZrO2/calcite, HZrO2/CaBT or HZrO2/CaZ mixture can effectively prevent the sedimentary P release, and the immobilization of mobile P in the sediment and the uptake of dissolved reactive P (DRP) from the interstitial water by the amendment material played a key role in the control of P release from sediment by the combined amendment. Capping sediment with HZrO2/calcite, HZrO2/CaBT or HZrO2/CaZ mixture also can effectively intercept sediment P release, and the formation of P static layer attributed to the uptake of interstitial water DRP and DGT (diffusive gradient in thin-films)-unstable P in the upper sediment by the capping material was a key to the inhibition of sedimentary P migration into the overlying water by the combined capping. The great majority of P immobilized by the HZrO2/calcite, HZrO2/CaBT or HZrO2/CaZ combined covering layer is stable P and it has a low re-releasing risk under dissolved oxygen-deficit and pH 5-9 condition. The stability of P bound by the combined covering layer was larger than that by the single HZrO2 covering layer. The results of this research show that the combined use of HZrO2 and calcite, HZrO2 and CaBT, or HZrO2 and CaZ as a capping material has great potential in the reduction of sediment P loading.

Combined amendment and capping of sediment with ferrihydrite and magnetite to control internal phosphorus release.

This study developed novel active capping systems with recycling convenience using ferrihydrite (Fh) combined with magnetite (Mag), and investigated the effectiveness and mechanism for the restriction of endogenous phosphorus movement from sediment into overlying water (OW) by the combined use of Fh and Mag. The Fh/Mag combined amendment effectively hindered endogenous phosphorus release from sediment to OW in dissolved oxygen (DO)-deficit environment, and the immobilization of diffusion gradient in thin film-labile phosphorus (LPDGT) and mobile phosphorus in the sediment played a key role in the control of endogenous phosphorus liberation by the Fh/Mag combined amendment. Combined capping sediment with Fh and Mag effectively hindered endogenous phosphorus release from sediment to OW in anoxic environment, and the inactivation of LPDGT in the upper sediment played a key part in the control of sediment phosphorus release by the Fh/Mag mixture capping. The stability of phosphorus immobilized by the Fh/Mag combined covering layer was related to its construction way, and the majority (around 90%) of P immobilized to the Fh/Mag mixture covering layer had low risk of release in common pH (5-9) and DO-deficit environments. The Fh/Mag mixture amendment or capping did not increase the risk of sediment iron release, and it also did not produce a large impact on the diversity and richness of bacterial community in the sediment. The combined utilization of Fh and Mag as a composite amendment or capping material to prevent the internal phosphorus from being moved to OW can make full use of their respective advantages. The Fh/Mag mixture capping wrapped by permeable fabric has high potential to reduce the risk of endogenous phosphorus from sediment into OW due to its advantages of high internal phosphorus release suppression efficiency, environmental friendliness, application convenience and sustainability.

Immobilization of lead, copper, cadmium, nickel, and zinc in sediment by red mud: adsorption characteristics, mechanism, and effect of dosage on immobilization efficiency.

The objective of this work was to determine the effect of dosage on the immobilization of lead (Pb), copper (Cu), cadmium (Cd), nickel (Ni), and zinc (Zn) in sediment by red mud (RM). To achieve this aim, the adsorption characteristics and mechanism of Pb, Cu, Cd, Ni, and Zn from aqueous solution on RM were studied at first, and then the influence of the RM dosage on the fractionation and leaching potential of Pb, Cu, Cd, Ni, and Zn in sediment was investigated. The results showed that RM possessed high adsorption capacities for Pb(II), Cu(II), Cd(II), Ni(II), and Zn(II) in aqueous solution. The maximum monolayer Pb(II), Cu(II), Cd(II), Ni(II), and Zn(II) adsorption capacities for RM derived from the Langmuir isotherm model were found to be 296, 39.2, 70.2, 46.0, and 50.7 mg/g, respectively. The addition of RM into sediment could effectively reduce the toxicity characteristic leaching procedure (TCLP)-leachable concentrations of Pb, Cu, Cd, Ni, and Zn in the sediment. The added RM could effectively immobilize the mobile (exchangeable, reducible, and oxidizable fractions) Pb in sediment by the conversion of the exchangeable and reducible fractions into the residual fraction, and it could effectively immobilize the mobile Cu, Cd, Ni, and Zn in sediment by the conversion of the exchangeable fraction into the residual fraction. The quantities of mobile Pb, Cu, Cd, and Ni immobilized by RM had a good linear relationship with the added RM. The above results suggest that RM is a promising amendment for the immobilization of mobile Pb, Cu, Cd, Ni, and Zn in sediment, and the linear relationship between the RM dosage and the quantities of immobilized Pb, Cu, Cd, and Ni by RM can be employed to determine the RM dosage required for the immobilization of mobile Pb, Cu, Cd, and Ni in sediment.

Contrasting effect of zirconium-, iron-, and zirconium/iron-modified attapulgites capping and amendment on phosphorus mobilization in sediment.

In this research, the sorption characteristics and mechanism of phosphate on zirconium-modified attapulgite (Zr-ATP), iron-modified attapulgite (Fe-ATP), and zirconium/iron co-modified attapulgite (Zr/Fe-ATP) prepared by a simple impregnation method were studied, and the impacts of Zr-ATP, Fe-ATP, and Zr/Fe-ATP amendment and capping on the migration of phosphorus (P) from sediments to overlying waters were investigated. The results showed that Zr-ATP and Zr/Fe-ATP possessed stronger adsorption ability for phosphate in aqueous solution than Fe-ATP. The ligand replacement of the hydroxyl group with the phosphate anion to form the inner-sphere phosphate complex played a crucial role in the adsorption process of phosphate on Zr-ATP, Fe-ATP, and Zr/Fe-ATP. Most of the phosphate ions bound by Zr-ATP and Zr/Fe-ATP were in the form of caustic soda solution-extractable inorganic P (NaOH-IP) and residual P (Res-P), and it is hard for these P species to be re-released into water under the circumstances of reducing environment and normal pH (5-9). The ratio of mobile P to total P of Fe-ATP loaded with phosphate was much higher than those of Zr-ATP and Zr/Fe-ATP loaded with phosphate, indicating that Fe-ATP-bound phosphate has a higher re-releasing risk than Zr-ATP-bound and Zr/Fe-ATP-bound phosphate. Zr-ATP, Fe-ATP, and Zr/Fe-ATP amendment all can reduce the releasing risk of P from sediments to overlying waters. The amendment of sediment with Zr-ATP and Zr/Fe-ATP can both induce the conversion of redox-sensitive P (BD-P) to NaOH-IP and Res-P in the sediment, making the phosphorus in the sediment more stable. However, the amendment of sediment with Fe-ATP can only induce the conversion of HCl-P to NaOH-IP in the sediment and had a negligible effect on the inorganic P activity in the sediment. Zr-ATP, Fe-ATP, and Zr/Fe-ATP capping all can reduce the risk of P release from sediment into the overlying water, and Zr-ATP and Zr/Fe-ATP capping had a better reduction efficiency of internal P liberation to the overlying water than Fe-ATP capping. Zr-ATP, Fe-ATP, and Zr/Fe-ATP capping all can give rise to the reduction of pore water SRP and diffusive gradient in thin-film (DGT)-labile P in the upper sediment. This is beneficial to the control of P releasing from sediment into the overlying water by the Zr-ATP, Fe-ATP, and Zr/Fe-ATP capping. The findings of this work suggest that Zr-ATP and Zr/Fe-ATP are promising active capping or amendment materials for internal P loading management in surface water bodies.

Effect of sediment burial depth on the control of sedimentary phosphorus release by iron/aluminum co-modified calcite and strategy for overcoming the negative effect of sediment burial.

After placing an active capping material on surface sediments, the capping layer will be buried by the newly formed sediment. In this research, the influence of sediment burial depth on the performance of iron/aluminum co-modified calcite (FeAlCAL) to suppress sedimentary phosphorus (P) release into overlaying water (OL-water) was studied. Furthermore, in order to find out the strategy for overcoming the negative effect of sediment burial, the efficiencies and mechanisms of three different FeAlCAL treatments (one-time FeAlCAL capping with 3 cm sediment burial, multiple FeAlCAL capping with 1 cm sediment burial, and amendment of top 3 cm sediment with FeAlCAL) in the inhibition of sediment P release were contrastively studied. The results showed that with the increase of sediment burial depth, the efficiency of FeAlCAL to block the release of sediment P into OL-water gradually decreased until the FeAlCAL lost the ability to hinder sediment-P release. In contrast to the one-time FeAlCAL capping in the presence of 3 cm sediment burial, the multiple FeAlCAL capping in the presence of 1 cm sediment burial and amendment of top 3 cm sediment with FeAlCAL both effectively prevented the release of P from sediment into OL-water. All results of this work suggest that although sediment burial can negatively affect the ability of FeAlCAL in the inhibition of sediment P release into OL-water and the negative effect becomes stronger as the sediment burial depth increases, the transformation of the application mode of FeAlCAL from one-time capping to multiple capping or from capping to amendment can overcome the negative influence of sediment burial.

Effect of application mode (capping and amendment) on the control of cadmium release from sediment by apatite/calcite mixture and its phosphorus release risk.

In this research, the influence of application mode (capping and amendment) on the control of cadmium (Cd) liberation from sediment by apatite/calcite mixture and its phosphorus release risk were investigated. The results showed that calcite addition had a limited effect on the speciation of Cd in sediment, but apatite addition had a significant impact on the fractionation of Cd in sediment. Apatite amendment could effectively immobilize the most readily mobilized Cd by transferring the acid-soluble fraction to the reducible and residual fractions. Apatite addition also could effectively reduce the concentration of toxicity characteristic leaching procedure (TCLP)-leachable Cd in sediment, and apatite had a much higher reduction efficiency of TCLP-leachable Cd than calcite. Apatite/calcite mixture capping could reduce the risk of Cd liberation from sediment into the overlying water, and the controlling efficiency of apatite/calcite mixture capping was higher than that of apatite/calcite mixture amendment. The effect of apatite/calcite mixture addition on the concentration of reactive soluble phosphorus (SRP) in the overlying water was limited. The introduction of calcite into the apatite capping layer could lower the risk of phosphorus release from apatite to the overlying water as compared to single apatite capping. However, the apatite/calcite mixture capping layer still had a relatively high risk of phosphorus liberation into the overlying water. Results of this work suggest that apatite/calcite mixture has a high potential to be used as a capping material to control Cd release from sediment from the perspective of controlling efficiency and application convenience.

Suppression of phosphorus release from sediment using lanthanum carbonate as amendment.

The performance of lanthanum carbonate (LC) pertaining to the adsorption of phosphate (HwPO4w-3) was investigated, and the possible adsorption mechanism was elucidated. The stabilization of HwPO4w-3 adsorbed to LC was evaluated. The influence of LC addition on the upward transport of phosphorus (P) from sediment to overlying water (OL-W) was studied, and the adsorption performance of HwPO4w-3 on the LC-amended sediment was explored. The results of this work indicated that LC performed well in the elimination of HwPO4w-3 from water in the pH range of 4 to 11, and the commercial and self-prepared LC samples afforded the maximum HwPO4w-3 adsorption capacities of 57.9 and 99.4 mg P/g, respectively, at pH 7. The presence of coexisting species including chloride, bicarbonate, and sulfate had a small influence on the HwPO4w-3 adsorption onto LC. The main HwPO4w-3 adsorption mechanism of LC at pH 7 was the ligand exchange reaction between carbonate and HwPO4w-3 forming the inner-sphere La-phosphate complexation. The self-synthesized LC exhibited much higher HwPO4w-3 adsorption performance than the commercial LC. The overwhelming majority (> 97.0%) of HwPO4w-3 adsorbed to LC primarily existed in the form of muriatic acid-extractable P, which has relatively low re-releasing risk. The addition of LC into sediment could significantly prevent the release of P from the sediment solid into the OL-W, thereby leading to a lower concentration level of reactive soluble P (RSP) in the OL-W compared with no LC treatment. The addition of LC into sediment could greatly improve the HwPO4w-3 uptake ability for the sediment, and the enhancement of HwPO4w-3 adsorption onto the sediment by the added LC increased as the increase of the amendment dosage and the initial HwPO4w-3 concentration. All results suggest that LC could serve as a promising amendment material for the control of sedimentary P release.

[Effect of the Combined Use of Denitrifying Bacteria, Calcium Nitrate, and Zirconium-Modified Zeolite on the Mobilization of Nitrogen and Phosphorus in Sediments and Evaluation of Its Nitrate-Nitrogen Releasing Risk].

In this work, the influence of an integrated method based on calcium nitrate, denitrifying bacteria, and zirconium-modified zeolite (CN+DB+ZZ) on the transport and transformation of nitrogen (N) and phosphorus (P) in sediments was investigated, and the risk of nitrate release from the calcium nitrate-injected sediment was evaluated. The effects of the single calcium nitrate injection (CN), calcium nitrate, and denitrifying bacteria combined treatment (CN+DB) and the combined treatment using calcium nitrate injection and zirconium-modified zeolite capping (CN+ZZ) on the mobilization of N and P in sediment were compared, and the nitrate releasing risk of these methods was also evaluated. The results indicated that although CN treatment could effectively control the P release from the sediment, this method could not effectively control the release of ammonium-nitrogen from sediment and has a high risk of releasing nitrate-nitrogen. The CN+DB combined method not only could effectively control the liberation of sedimentary P but also reduce the risk of nitrate-nitrogen release from the calcium nitrate-injected sediment compared with the single CN method. However, the CN+DB combined method could not effectively control the release of ammonium-nitrogen from the sediment. The CN+ZZ combined treatment not only could effectively prevent the release of sedimentary P but could also greatly reduce the release of ammonium-nitrogen from the sediment. However, the CN+ZZ combined method could result in a substantial release of nitrate-nitrogen from the calcium nitrate-injected sediment. The CN+DB+ZZ combined technology could effectively control the release of P from sediment as well as greatly reduce the risk of ammonium-nitrogen release from the sediment. Furthermore, the CN+DB+ZZ combined method resulted in a significant reduction of nitrate-nitrogen released from the calcium nitrate-injected sediment compared with the CN and CN+ZZ treatment methods. The prevention of the dissolution of the P-bound iron oxide/hydroxide in the sediment, the reduction of redox-sensitive P in sediment, and the improvement of the phosphate and ammonium adsorption abilities of sediment by the CN+DB+ZZ combined method is critical to control the release of phosphorus and ammonium-nitrogen from sediment using this method. Results of this study reveal that the CN+DB+ZZ combined technology could be a promising method for the control of phosphorus and ammonium-nitrogen release from sediments.

[Combined Use of Zirconium-Modified Bentonite Capping and Calcium Nitrate Addition to Control the Release of Phosphorus from Sediments].

In this study, sediment incubation experiments were carried out to investigate the efficiency and mechanism of the control of phosphorus (P) release from sediments. The results showed that under anoxic conditions, P could be released from the sediment into the pore water first and then the dissolved P in the pore water could be transported into the overlying water, leading to high concentrations of soluble reactive P (SRP) and diffusive gradient in thin-films (DGT)-labile P in the overlying water. However, the combined use of calcium nitrate (CN) addition and zirconium-modified bentonite (ZB) capping could effectively control the release of P from sediment, resulting in the low concentrations of SRP and DGT-labile P in the overlying water. Furthermore, the combined use of CN addition and ZB capping could significantly decrease the concentrations of SRP and DGT-labile P in the sediment. In addition, the combined utilization of CN addition and ZB capping also could result in a reduction of redox sensitive P (BD-P) in the uppermost sediment layer. The reduction of pore water SRP, DGT-labile P, and BD-P in sediment solids is of great importance to the control of sediment-P liberation by the combined use of CN addition and ZB capping. The reduction efficiency of overlying water SRP by combined CN addition/ZB capping technology was higher than that of single CN addition technology. Compared to that of single CN addition technology, the reduction efficiencies of pore water SRP, SRP diffusion flux across the sediment/overlying water interface (SWI), and BD-P in the sediment by the combined use of CN addition and ZB capping were also higher. The combined technology based on CN addition and ZB capping had a higher reduction efficiency of overlying water SRP during the late stage of sediment remediation than the single technology based on ZB capping, and the former had higher reduction efficiencies of pore water SRP, DGT-labile P, and SRP diffusion flux across the SWI and apparent P diffusion flux through the SWI than the latter. The results of this work indicate that the combined use of CN addition and ZB capping is a very promising method for the control of P release from sediments.