Polymer Coatings Affect Transport and Remobilization of Colloidal Activated Carbon in Saturated Sand Columns: Implications for In Situ Groundwater Remediation.

Colloidal activated carbon (CAC) is an emerging technology for the in situ remediation of groundwater impacted by per- and polyfluoroalkyl substances (PFAS). In assessing the long-term effectiveness of a CAC barrier, it is crucial to evaluate the potential of emplaced CAC particles to be remobilized and migrate away from the sorptive barrier. We examine the effect of two polymer stabilizers, carboxymethyl cellulose (CMC) and polydiallyldimethylammonium chloride (PolyDM), on CAC deposition and remobilization in saturated sand columns. CMC-modified CAC showed high mobility in a wide ionic strength (IS) range from 0.1 to 100 mM, which is favorable for CAC delivery at a sufficient scale. Interestingly, the mobility of PolyDM-modified CAC was high at low IS (0.1 mM) but greatly reduced at high IS (100 mM). Notably, significant remobilization (release) of deposited CMC-CAC particles occurred upon the introduction of solution with low IS following deposition at high IS. In contrast, PolyDM-CAC did not undergo any remobilization following deposition due to its favorable interactions with the quartz sand. We further elucidated the CAC deposition and remobilization behaviors by analyzing colloid-collector interactions through the application of Derjaguin-Landau-Verwey-Overbeek theory, and the inclusion of a discrete representation of charge heterogeneity on the quartz sand surface. The classical colloid filtration theory was also employed to estimate the travel distance of CAC in saturated columns. Our results underscore the roles of polymer coatings and solution chemistry in CAC transport, providing valuable guidelines for the design of in situ CAC remediation with maximized delivery efficiency and barrier longevity.

Sulfidation of Iron-Based Materials: A Review of Processes and Implications for Water Treatment and Remediation.

Iron-based materials used in water treatment and groundwater remediation-especially micro- and nanosized zerovalent iron (nZVI)-can be more effective when modified with lower-valent forms of sulfur (i.e., "sulfidated"). Controlled sulfidation for this purpose (using sulfide, dithionite, etc.) is the main topic of this review, but insights are derived by comparison with related and comparatively well-characterized processes such as corrosion of iron in sulfidic waters and abiotic natural attenuation by iron sulfide minerals. Material characterization shows that varying sulfidation protocols (e.g., concerted or sequential) and key operational variables (e.g., S/Fe ratio and sulfidation duration) result in materials with structures and morphologies ranging from core-shell to multiphase. A meta-analysis of available kinetic data for dechlorination under anoxic conditions, shows that sulfidation usually increases dechlorination rates, and simultaneously hydrogen production is suppressed. Therefore, sulfidation can greatly improve the efficiency of utilization of reducing equivalents for contaminant removal. This benefit is most likely due to inhibited corrosion as a result of sulfidation. Sulfidation may also favor desirable pathways of contaminant removal, such as (i) dechlorination by reductive elimination rather than hydrogenolysis and (ii) sequestration of metals as sulfides that could be resistant to reoxidation. Under oxic conditions, sulfidation is shown to enhance heterogeneous catalytic oxidation of contaminants. These net effects of sulfidation on contaminant removal by iron-based materials may substantially improve their practical utility for water treatment and remediation of contaminated groundwater.

Current state of in situ subsurface remediation by activated carbon-based amendments.

The last decade has seen a growing interest in applying activated carbon (AC)-based amendments for in situ subsurface remediation of organic contaminants such as chlorinated solvents and petroleum hydrocarbons. This remedial technology has been promoted by several major AC-based product vendors on the market. These products involve impregnation or co-application of chemical or biological additives to facilitate various contaminant degradation processes in conjunction with contaminant adsorption. During field applications, rapid contaminant removal and limited rebound after emplacement have often been reported and considered as two major advantages for this remedial technology. Nevertheless, questions remain to be answered regarding its true effectiveness and longevity given the lack of subsequent field characterizations and evidence of the degradation process, especially biodegradation. Additional uncertainties reside in how subsurface heterogeneity may affect the design, implementation and performance monitoring of this technology. In light of these uncertainties, this review presents an independent analysis that focuses on both the scientific and practical aspects of AC-based remedial technology for in situ subsurface remediation by gathering and synthesizing the scientific knowledge and practical lessons from a broad range of contaminant removal processes involving adsorption and/or degradation. The analysis showed that the scientific soundness of combining adsorption and degradation proposed for all the AC-based products is well supported by the literature on ex situ treatment. However, the in situ effectiveness might be affected by additional factors, such as geological heterogeneity, amendment transport and distribution, and total contaminant mass, which require more thorough and quantitative evaluation. Overall, the technology may provide a viable tool in addressing major remediation challenges encountered in current practice, such as mitigation of back diffusion from residual sources in low permeability zones and treatment of low concentration plumes.

Sulfidation of Nano Zerovalent Iron (nZVI) for Improved Selectivity During In-Situ Chemical Reduction (ISCR).

The high reactivity of nano zerovalent iron (nZVI) leads to inefficient treatment due to competition with various natural reductant demand (NRD) processes, especially the reduction of water to hydrogen. Here we show that this limitation can be alleviated by sulfidation (i.e., modification by reducing sulfur compounds). nZVI synthesized on carboxylmethylcelluose (CMC-nZVI) was sulfidated with either sulfide or dithionite. The reactivity of the resulting materials was examined with three complementary assays: (i) direct measurement of hydrogen production, (ii) reduction of a colorimetric redox probe (indigo disulfonate, I2S), and (iii) dechlorination of trichloroethylene (TCE). The results indicate that sulfidation at S/Fe molar ratios of ≥0.3, effectively eliminates reaction with water, but retains significant reactivity with TCE. However, sulfidation with sulfide leaves most of the nZVI as Fe(0), whereas dithionite converts a majority of the nZVI to FeS (thus consuming much of the reducing capacity originally provided by the Fe(0)). Simplified numerical models show that the reduction kinetics of I2S and TCE are mainly dependent on the initial reducing equivalents and that the TCE reduction rate is affected by the aging of FeS. Overall, the results suggest that pretreatment of nZVI with reducing sulfur compounds could result in substantial improvement in nZVI selectivity.

Chemical Reactivity Probes for Assessing Abiotic Natural Attenuation by Reducing Iron Minerals.

Increasing recognition that abiotic natural attenuation (NA) of chlorinated solvents can be important has created demand for improved methods to characterize the redox properties of the aquifer materials that are responsible for abiotic NA. This study explores one promising approach: using chemical reactivity probes (CRPs) to characterize the thermodynamic and kinetic aspects of contaminant reduction by reducing iron minerals. Assays of thermodynamic CRPs were developed to determine the reduction potentials (ECRP) of suspended minerals by spectrophotometric determination of equilibrium CRP speciation and calculations using the Nernst equation. ECRP varied as expected with mineral type, mineral loading, and Fe(II) concentration. Comparison of ECRP with reduction potentials measured potentiometrically using a Pt electrode (EPt) showed that ECRP was 100-150 mV more negative than EPt. When EPt was measured with small additions of CRPs, the systematic difference between EPt and ECRP was eliminated, suggesting that these CRPs are effective mediators of electron transfer between mineral and electrode surfaces. Model contaminants (4-chloronitrobenzene, 2-chloroacetophenone, and carbon tetrachloride) were used as kinetic CRPs. The reduction rate constants of kinetic CRPs correlated well with the ECRP for mineral suspensions. Using the rate constants compiled from literature for contaminants and relative mineral reduction potentials based on ECRP measurements, qualitatively consistent trends were obtained, suggesting that CRP-based assays may be useful for estimating abiotic NA rates of contaminants in groundwater.

Effects of Sulfidation, Magnetization, and Oxygenation on Azo Dye Reduction by Zerovalent Iron.

Applications of zerovalent iron (ZVI) for water treatment under aerobic conditions include sequestration of metals (e.g., in acid mine drainage) and decolorization of dyes (in wastewaters from textile manufacturing). The processes responsible for contaminant removal can be a complex mixture of reduction, oxidation, sorption, and coprecipitation processes, which are further complicated by the dynamics of oxygen intrusion, mixing, and oxide precipitation. To better understand such systems, the removal of an azo dye (Orange I) by micron-sized granular ZVI at neutral pH was studied in open (aerobic) stirred batch reactors, by measuring the kinetics of Orange I decolorization and changes in "geochemical" properties (DO, Fe(II), and Eh), with and without two treatments that might improve the long-term performance of this system: sulfidation by pretreatment with sulfide and magnetization by application of a weak magnetic field (WMF). The results show that the changes in solution chemistry are coupled to the dynamics of oxygen intrusion, which was modeled as analogous to dissolved oxygen sag curves. Both sulfidation and magnetization increased Orange I removal rates 2.4-71.8-fold, but there was little synergistic benefit to applying both enhancements together. Respike experiments showed that the enhancement from magnetization carries over from magnetization to sulfidation, but not the reverse.

Field Deployable Chemical Redox Probe for Quantitative Characterization of Carboxymethylcellulose Modified Nano Zerovalent Iron.

Nano zerovalent iron synthesized with carboxymethylcelluose (CMC-nZVI) is among the leading formulations of nZVI currently used for in situ groundwater remediation. The main advantage of CMC-nZVI is that it forms stable suspensions, which are relatively mobile in porous media. Rapid contaminant reduction by CMC-nZVI is well documented, but the fate of the CMC-nZVI (including "aging" and "reductant demand") is not well characterized. Improved understanding of CMC-nZVI fate requires methods with greater specificity for Fe(0), less vulnerability to sampling/recovery artifacts, and more practical application in the field. These criteria can be met with a simple and specific colorimetric approach using indigo-5,5'-disulfonate (I2S) as a chemical redox probe (CRP). The measured stoichiometric ratio for reaction between I2S and nZVI is 1.45 ± 0.03, suggesting complete oxidation of nZVI to Fe(III) species. However, near pH 7, reduction of I2S is diagnostic for Fe(0), because aqueous Fe(II) reduces I2S much more slowly than Fe(0). At that pH, adding Fe(II) increased I2S reduction rates by Fe(0), consistent with depassivation of nZVI, but did not affect the stoichiometry. Using the I2S assay to quantify changes in the Fe(0) content of CMC-nZVI, the rate of Fe(0) oxidation by water was found to be orders of magnitude faster than previously reported values for other types of nZVI.

Oxidative remobilization of technetium sequestered by sulfide-transformed nano zerovalent iron.

Our previous study showed that formation of TcS2-like phases is favored over TcO2 under sulfidic conditions stimulated by nano zerovalent iron. This study further investigates the stability of Tc(IV) sulfide upon reoxidation by solution chemistry, solid phase characterization, and X-ray absorption spectroscopy. Tc dissolution data showed that Tc(VII) reduced by sulfide-transformed nZVI has substantially slower reoxidation kinetics than Tc(VII) reduced by nZVI only. The initial inhibition of Tc(IV) dissolution at S/Fe = 0.112 is due to the redox buffer capacity of FeS, which is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution kinetics. The role of FeS in inhibiting Tc oxidation is further supported by the Mössbauer spectroscopy and micro X-ray diffraction data at S/Fe = 0.112, showing persistence of FeS after 24-h oxidation but complete oxidation after 120-h oxidation. X-ray absorption spectroscopy data for S/Fe = 0.011 showed significantly increasing percentages of TcS2 in the solid phase after 24-h oxidation, indicating stronger resistance of TcS2 to oxidation. At S/Fe = 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 after 120-h oxidation. Given that no apparent Tc dissolution occurred during this period, the speciation transformation might play a secondary role in hindering Tc oxidation. Collectively, the results indicate that sequestrating Tc as TcS2 under stimulated sulfate reduction is a promising strategy to improve the long-term stability of reduced Tc in subsurface remediation.

Biochar and surfactant synergistically enhanced PFAS destruction in UV/sulfite system at neutral pH.

The UV/sulfite-based advanced reduction process (ARP) emerges as an effective strategy to combat per- and polyfluoroalkyl substances (PFAS) pollution in water. Yet, the UV/sulfite-ARP typically operates at highly alkaline conditions (e.g., pH > 9 or even higher) since the generated reductive radicals for PFAS degradation can be quickly sequestered by protons (H+). To overcome the associated challenges, we prototyped a biochar-surfactant-system (BSS) to synergistically enhance PFAS sorption and degradation by UV/sulfite-ARP. The degradation and defluorination efficiencies of perfluorooctanoic acid (PFOA) depended on solution pH, and concentrations of surfactant (cetyltrimethylammonium bromide; CTAB), sulfite, and biochar. At high pH (8-10), adding biochar and BSS showed no or even small inhibitory effect on PFOA degradation, since the degradation efficiencies were already high enough that cannot be differentiated. However, at acidic and neutral pH (6-7), an evident enhancement of PFOA degradation and defluorination efficiencies occurred. This is due to the synergies between biochar and CTAB that create favorable microenvironments for enhanced PFOA sorption and deeper destruction by prolonging the longevity of reductive radicals (e.g., SO3•-), which is less affected by ambient pH conditions. The performance of UV/sulfite/BSS was further optimized and used for the degradation of four PFAS. At the optimal experimental condition, the UV/sulfite/BSS system can completely degrade PFOA with >30% defluorination efficiency for up to five continuous cycles (n = 5). Overall, our BSS provides a cost-effective and sustainable technique to effectively degrade PFAS in water under environmentally relevant pH conditions. The BSS-enabled ARP technique can be easily tied into PFAS treatment train technology (e.g., advanced oxidation process) for more efficient and deeper defluorination of various PFAS in water.

Groundwater solutes influence the adsorption of short-chain perfluoroalkyl acids (PFAA) to colloidal activated carbon and impact performance for in situ groundwater remediation.

Subsurface injection of colloidal activated carbon (CAC) is an in situ remediation strategy for perfluoroalkyl acids (PFAA), but the influence of groundwater solutes on longevity is uncertain, particularly for short-chain PFAA. We quantify the impact of inorganic anions, dissolved organic matter (DOM), and stabilizing polymer on PFAA adsorption to a commercial CAC. Surface characterization supported PFAA chain-length dependent adsorption results and mechanisms are provided. Inorganic anions decreased adsorption for short-chain PFAA (<7 perfluorinated carbons) due to competitive effects, while long-chain PFAA (≥ 7 perfluorinated carbons) were less impacted. DOM decreased adsorption of all PFAA in a chain-length dependent manner. High DOM concentrations (10 mg/L, ∼5 mg OC/L) decreased PFOA adsorption by a factor of 2, PFPeA by one order of magnitude, and completely hindered PFBA adsorption. High MW DOM has less impact on short-chain PFAA than low MW DOM, possibly due to differences in the ability to access CAC micropores. Low DOM concentrations (1 mg/L, ∼0.5 mg OC/L) did not impact adsorption. CMC (90 kDa average MW) had negligible impact on PFAA adsorption likely due to minimal CAC surface coverage. Longevity modeling demonstrated that groundwater solutes limit the capacity for PFAA in a CAC barrier, particularly for short-chain PFAA.

Field-scale transport and transformation of carboxymethylcellulose-stabilized nano zero-valent iron.

The fate of nano zerovalent iron (nZVI) during subsurface injection was examined using carboxymethylcellulose (CMC) stabilized nZVI in a very large three-dimensional physical model aquifer with detailed monitoring using multiple, complementary detection methods. A fluorescein tracer test in the aquifer plus laboratory column data suggested that the very-aggressive flow conditions necessary to achieve 2.5 m of nZVI transport could be obtained using a hydraulically constrained flow path between injection and extraction wells. However, total unoxidized nZVI was transported only about 1 m and <2% of the injected nZVI concentration reached that distance. The experimental data also indicated that groundwater flow changed during injection, likely due to hydrogen bubble formation, which diverted the nZVI away from the targeted flow path. The leading edge of the iron plume became fully oxidized during transport. However, within the plume, oxidation of nZVI decreased in a fashion consistent with progressive depletion of aquifer "reductant demand". To directly quantify the extent of nZVI transport, a spectrophotometric method was developed, and the results indicated that deployment of unoxidized nZVI for groundwater remediation will likely be difficult.

Reductive sequestration of pertechnetate (99TcO4⁻) by nano zerovalent iron (nZVI) transformed by abiotic sulfide.

Under anoxic conditions, soluble pertechnetate (99TcO4⁻) can be reduced to less soluble TcO2·nH2O, but the oxide is highly susceptible to reoxidation. Here we investigate an alternative strategy for remediation of Tc-contaminated groundwater whereby sequestration as Tc sulfide is favored by sulfidic conditions stimulated by nano zerovalent iron (nZVI). nZVI was pre-exposed to increasing concentrations of sulfide in simulated Hanford groundwater for 24 h to mimic the onset of aquifer biotic sulfate reduction. Solid-phase characterizations of the sulfidated nZVI confirmed the formation of nanocrystalline FeS phases, but higher S/Fe ratios (>0.112) did not result in the formation of significantly more FeS. The kinetics of Tc sequestration by these materials showed faster Tc removal rates with increasing S/Fe between 0 and 0.056, but decreasing Tc removal rates with S/Fe > 0.224. The more favorable Tc removal kinetics at low S/Fe could be due to a higher affinity of TcO4⁻ for FeS than iron oxides, and electron microscopy confirmed that the majority of the Tc was associated with FeS phases. The inhibition of Tc removal at high S/Fe appears to have been caused by excess HS(-). X-ray absorption spectroscopy revealed that as S/Fe increased, the pathway for Tc(IV) formation shifted from TcO2·nH22 to Tc sulfide phases. The most substantial change of Tc speciation occurred at low S/Fe, coinciding with the rapid increase in Tc removal rate. This agreement further confirms the importance of FeS in Tc sequestration.

Reactivity of Fe/FeS nanoparticles: electrolyte composition effects on corrosion electrochemistry.

Zerovalent iron nanoparticles (Fe(0) NPs or nZVI) synthesized by reductive precipitation in aqueous solution (Fe/FeO) differ in composition and reactivity from the NPs obtained by reductive precipitation in the presence of a S-source such as dithionite (Fe/FeS). To compare the redox properties of these types of NPs under a range of environmentally relevant solution conditions, stationary powder disk electrodes (PDEs) made from Fe/FeO and Fe/FeS were characterized using a series of complementary electrochemical techniques: open-circuit chronopotentiometry (CP), linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). The passive films on these materials equilibrate within minutes of first immersion and do not show further breakdown until >1 day of exposure. During this period, the potentials and currents measured by LPR and LSV suggest that Fe/FeS undergoes more rapid corrosion and is more strongly influence by solution chemical conditions than Fe/FeO. Chloride containing media were strongly activating and natural organic matter (NOM) was mildly passivating for both materials. These effects were also seen in the impedance data obtained by EIS, and equivalent circuit modeling of the electrodes composed of these powders suggested that the higher reactivity of Fe/FeS is due to greater abundance of defects in its passive film.

Natural Biodegradation of Vinyl Chloride and cis-Dichloroethene in Aerobic and Suboxic Conditions.

Chlorinated ethene (CE) groundwater contamination is commonly treated through anaerobic biodegradation (i.e., reductive dechlorination) either as part of an engineered system or through natural attenuation. Aerobic biodegradation has also been recognized as a potentially significant pathway for the removal of the lower CEs cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC). However, the role of aerobic biodegradation under low oxygen conditions typical of contaminated groundwater is unclear. Bacteria capable of aerobic VC biodegradation appear to be common in the environment, while aerobic biodegradation of cDCE is less common and little is known regarding the organisms responsible. In this study, we investigate the role of aerobic cDCE and VC biodegradation in a mixed contaminant plume (including CEs, BTEX, and ketones) at Naval Air Station North Island, Installation Restoration Site 9. Sediment and groundwater collected from the plume source area, mid-plume, and shoreline were used to prepare microcosms under fully aerobic (8 mg/L dissolved oxygen (DO)) and suboxic (< 1 mg/L DO) conditions. In the shoreline microcosms, VC and cDCE were rapidly degraded under suboxic conditions (100% and 77% removal in < 62 days). In the suboxic VC microcosms, biodegradation was associated with a > 5 order of magnitude increase in the abundance of functional gene etnE, part of the aerobic VC utilization pathway. VC and cDCE were degraded more slowly under fully aerobic conditions (74% and 30% removal) in 110 days. High-throughput 16S rRNA and etnE sequencing suggest the presence of novel VC- and cDCE-degrading bacteria. These results suggest that natural aerobic biodegradation of cDCE and VC is occurring at the site and provide new evidence that low (< 1 mg/L) DO levels play a significant role in natural attenuation of cDCE and VC.

Quantifying the efficiency and selectivity of organohalide dechlorination by zerovalent iron.

The efficiency and selectivity of zerovalent iron-based treatments for organohalide contaminated groundwater can be quantified by accounting for redistribution of electrons derived from oxidation of Fe0. Several types of efficiency are reviewed, including (i) the efficiency of Fe(0) utilization, εFe(0), (ii) the electron efficiency of target contaminant reduction, εe, and (iii) the electron efficiency of natural reductant demand (NRD) involving H2O, O2, and co-contaminants such as nitrate, εNRD. Selectivity can then be calculated by using εe/εNRD. Of particular interest is εe and the key to its determination is measuring the total quantity of electrons provided by Fe0 oxidation, which can be based on either the loss of Fe(0), the formation of Fe(ii)/Fe(iii), or the composition of the total reaction products. Recently, many data have accumulated on εe for the treatment of various chlorinated solvents (esp. trichloroethylene, TCE) by zerovalent iron (ZVI), and analysis of these data shows that ZVI particle properties (e.g., stabilization with polymers, bimetallic modification, sulfidation, etc.) and other operational factors have variable effects on εe. Of particular interest is that pre-exposure of ZVI to reduced sulfur species (i.e., sulfidation) consistently improves the εe of contaminant reduction, mainly by suppressing the reduction of water.

Dynamic interactions between sulfidated zerovalent iron and dissolved oxygen: Mechanistic insights for enhanced chromate removal.

Recent research on contaminant removal by zerovalent iron (ZVI) has evolved from investigating simple model systems to systems that encompass increased dimensions of complexity. Sulfidation and aerobic conditions are two of the most broadly relevant complications. Combining these two, this study investigated the dynamic interactions between sulfidated microscale ZVI and dissolved O2, for removal of Cr(VI), a model contaminant for metals and metalloids. The results show that the coupling of sulfidation and oxygenation significantly improves Cr removal, which is attributed to enhanced Fe(II) production that resulted from accelerated corrosion of Fe(0). The Cr(VI) removal rate increased with increasing O2 saturation from 0% to 100% but showed a bimodal dependence on the S/Fe ratio. At the optimal S/Fe ratio, the ZVI exhibits a highly porous surface morphology, which, according to prior literature on sulfur induced corrosion, promotes corrosion. In addition, a novel time series correlation was developed between aqueous Fe(II) and Cr(VI) based on data collected in the presence and absence of 1,10-phenanthroline, to probe for changes of reductants during the reaction time course. The analysis indicated that Fe(0) was responsible for the initial small amount of Cr(VI) removal, which then transitioned to a phase controlled by surface Fe(II). The slopes of the time series correlations during the latter phase of the reaction vary with experimental conditions but are mostly much higher than the theoretical stoichiometric ratio between Cr(VI) and Fe(II) (i.e., 0.33), indicating that Fe(II) regeneration contributes significantly to Cr removal.

Methods for characterizing the fate and effects of nano zerovalent iron during groundwater remediation.

The emplacement of nano zerovalent iron (nZVI) for groundwater remediation is usually monitored by common measurements such as pH, total iron content, and oxidation-reduction potential (ORP) by potentiometry. However, the interpretation of such measurements can be misleading because of the complex interactions between the target materials (e.g., suspensions of highly reactive and variably aggregated nanoparticles) and aquifer materials (sediments and groundwater), and multiple complications related to sampling and detection methods. This paper reviews current practice for both direct and indirect characterizations of nZVI during groundwater remediation and explores prospects for improving these methods and/or refining the interpretation of these measurements. To support our recommendations, results are presented based on laboratory batch and column studies of nZVI detection using chemical, electrochemical, and geophysical methods. Chemical redox probes appear to be a promising new method for specifically detecting nZVI, based on laboratory tests. The potentiometric and voltammetric detections of iron nanoparticles, using traditional stationary disc electrodes, rotating disc electrodes, and flow-through cell disc electrodes, provide insight for interpreting ORP measurements, which are affected by solution chemistry conditions and the interactions between iron nanoparticles and the electrode surface. The geophysical methods used for characterizing ZVI during groundwater remediation are reviewed and its application for nZVI detection is assessed with results of laboratory column experiments.