In flooded soils, soil–waterinterface (SWI) is thekey zone controlling biogeochemical dynamics. Chemical species andconcentrations vary greatly at micro- to cm-scales. Techniques ableto track these changing element profiles both in space and over timewith appropriate resolution are rare.

Here, we report a patent-pendingtechnique, the Integrated Porewater Injection (IPI) sampler, whichis designed for soil porewater sampling with minimum disturbance tosaturated soil environment. IPI sampler employs a single hollow fibermembrane tube to passively sample porewater surrounding the tube.When working, it can be integrated into the sample introduction system,thus the sample preparation procedure is dramatically simplified.In this study, IPI samplers were coupled to ICP-MS at data-only mode.The limits of detection of IPI-ICP-MS for Ni, As, Cd, Sb, and Pb were0.12, 0.67, 0.027, 0.029, and 0.074 μgL –1, respectively. Furthermore, 25 IPI samplers were assembled intoan SWI profiler using 3D printing in a one-dimensional array. TheSWI profiler is able to analyze element profiles at high spatial resolution(∼2 mm) every ≥24 h.

When deployed in arsenic-contaminatedpaddy soils, it depicted the distributions and dynamics of multipleelements at anoxic–oxic transition. The results show that theSWI profiler is a powerful and robust technique in monitoring dynamicsof element profile in soil porewater at high spatial resolution. Themethod will greatly facilitate studies of elements behaviors in sedimentsof wetland, rivers, lakes, and oceans. IntroductionAquaticsediments play an important role as sinks for metals andmetalloids. The chemical speciation andmobility of elements are mainly controlled by the redox condition,pH, and organic matter content of the sediments. − Under naturalconditions, a redox transition occurs along the soil–waterinterface (SWI), and the biogeochemical characters vary at the mmscale in sediment. The element profilealong SWI varies when the external environment changes (e.g., pH,seasonal wet–dry cycle, exogenous pollutants introduction,microbial degradation, and wetland plant roots activity).

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− For example, arsenic (As) in soils is immobilized by mineral oxidesadsorption under oxidizing conditions, but mobilized by the desorptionof As from mineral oxides under reducing conditions., The redox changes along the SWI result in a distinct change of Asconcentration in a saturated soil profile. As a gate controlling themass exchange between the sediment and waterbody, it has always beenof great interest to study the spatial as well as the temporal distributionof elements along the SWI at high-resolution. However, a deep understandingof the elemental behavior in the environment has been hindered todate by the techniques available to sample this zone.Many techniqueshave been developed to study the behavior of elementsalong the SWI. Initially, slicing of frozen soil cores under anaerobicconditions was used., However, the soil slicing method is destructive, complex, and easilycontaminated. More recent work has focusedon nondestructive sampling methods. The rhizon sampler is a typicalnondestructive method that is at low cost and easy to operate. − When the samplers are placed horizontally along a profile, theycan measure the vertical distribution of elements.

However, the sampling zone of rhizon samplers is poorlydefined and generally greater than 1 cm, its application in high-resolutionSWI studies is limited.Compared to rhizon samplers, peeper,diffusive equilibration inthin films (DET), and diffusive gradient in thin-films (DGT) are muchpowerful.,− Peeper and DET/DGT probes passively sample the solutes in porewaterthrough diffusion/adsorption. When equilibrated, the liquid or gelis removed for element mapping analysis. The techniques have beenused to map elements with high spatial resolution (μm to cmlevel). Although peeper and DET/DGT are powerful in mapping elementprofile, they can only be used once after deployment, which limitsthe application of the technique in tracking temporal element change.In this study, a novel technique, calledIntegrated Porewater Injection(IPI) sampler, was developed to map spatial and temporal distributionof elements along the SWI. The IPI sampler uses a single hollow fibermembrane tube for passive sampling and active sample injection, thusthe workload for sample preparation is minimized. We investigatedthe limit of detection (LOD), influences of carrier solution and humcacid (HA), and the characteristics of time-dependent diffusion acrossthe sampling tube.

We also reported the integration of an array ofIPI samplers (SWI profiler) into a device that enables one-dimensionalelement profiling. The performance of SWI profiler was evaluatedin field-collected paddy soils under a changing anoxic–oxicenvironment by pumping N 2 or air. Reagentsand MaterialsThe chemicals used in this studywere of analytical or electronic grade and supplied by Aladdin ChemicalReagent Co., Ltd. (Shanghai, China), unless stated otherwise. Calibrationstandards, including nickel (Ni), arsenic (As), cadmium (Cd), antimony(Sb), and lead (Pb), were purchased from Guobiao (Beijing) Testing& Certification Co., Ltd.

(Beijing, China). Humic acid (HA) wasprovided by Alfa Aesar (catalog # 41747). All solutions were preparedwith ultrapure water (18.2 MΩ cm, Millipore Corp., Bedford,U.S.A.) deoxygenated by purging with pure N 2 for more than4 h. The sampling tube is made of a hollow fiber membrane tube (inner× outer diameter = 1.0 × 2.0 mm 2, polyvinylidenefluoride, Motimo Membrane Technology Co., Ltd., Tianjin, China).

Themembrane has a pore size of 0.05 μm, and pore rate of 70–80%.All the materials were ultrasonic washed with 2% HNO 3 and1% Decon solution for 15 min, respectively, and rinsed five timeswith ultrapure water. All the narrow tubes were oven-dried at 40 °Cbefore use.The soil samples used in the study were collectedfrom paddy fields in Gan Zhou (GZ, 25°30 ’N, 114°36′E)and Qing Yuan (QY, 23°35′N, 113°20′E), China.The top 20 cm of soil was sampled. Soil samples were wet sieved througha 1 mm diameter sieve. The soil characteristics are shown in of the. IPI SamplerDesign and SWI Profiler AssemblyThe structureof a typical IPI sampler is shown in A (Tidu Inc. Suzhou, China). The IPI samplercontains four components: (1) the hollow fiber membrane tube (20 mmin length), with a volume of 16 μL; (2) the diffusion depressor(0.3 × 0.8 × 5 mm 3, inner × outer diameter× length, PTFE); 3.

Pipe (silica tube, 0.5 × 1.5 ×180 mm 3, inner × outer diameter × length), witha volume of 35 μL; 4. Cap (carbon fiber, 0.8 × 20 mm 2, diameter × length). The hollow fiber membrane servesas a passive sampling tube during the sample collection (loading)stage. The diffusion depressor is designed to suppress the side diffusionof solutes from the hollow fiber membrane tube to the conduits throughnarrowing their connection. When connected to ICP-MS, the porewatersample in hollow fiber membrane tube is pumped out through the conduits.To avoid the negative influence of oxygen and dust in atmosphere,a carbon fiber cap is used to seal IPI sampler during sample loadingstage.

To extract soil porewater at different depth along SWI, SWIprofiler was used. An SWI profiler is consisted of 25 IPI samplers,which are assembled side by side in a 3D printed holder (C). The IPI samplerand SWI profiler were stored in carrier solution before use.

The Working Procedure ofIPI SamplerOnce the IPI sampleris deployed into solution or saturated soil, the small molecules andions diffuse into the hollow fiber membrane tube through the membrane(passive sampling stage, A). When equilibrium state is reached, the solutioninside the tubes is introduced into ICP-MS (NexION 350X, PerkinElmer,Inc., Shelton, CT U.S.A.) (active sample introduction stage, B). When introducingthe samples into ICP-MS, the caps were removed; the IPI sampler wasintegrated into the sampling system by replacing the sample loop ina six-way valve. The sample solution in an IPI sampler is pumped byICP-MS peristaltic pump at the speed of 24 rpm.

Twenty μgL –1 rhodium in 4% HNO 3 was used as the internalstandard. The ICP-MS conditions were as follows: STD mode; data onlyanalysis; RF power 1600W; plasma gas flow rate 15 Lmin –1; auxiliary gas flow 1.2 Lmin –1; nebulizedgas flow 0.94 Lmin –1; the uptake flow rateis 0.5 mLmin –1; and nickel sampling and skimmercones were used. Carrier Solution TestThe IPI samplerswere deployedin the 10 μgL –1 Ni, As, Cd, Sb,and Pb solution before test. Six kinds of matrix condition weretested: (i) ultrapure water in acidic condition (pH 1); (ii) ultrapurewater in near-neutral condition (pH 6); (iii) 10 mM NaNO 3 in pH 1; (iv) 10 mM NaNO 3 in pH 6; (v) 10 mM NaCl inpH 1; and (vi) 10 mM NaCl in pH 6.

The solution pH was adjusted byusing NaOH or HNO 3.The carrier effect of ultrapurewater and 10 mM NaCl carrier solutions were also tested in near-neutral floodedsoils. The IPI samplers were deployed at a depth of 2 cm in two floodedpaddy soils (GZ and QY), respectively.

After 24 h incubation, thesample was analyzed by directly introducing to ICP-MS. Time-Dependent Responseand Calibration CurveThe time-dependentresponse of IPI samplers was conducted in acidic and near-neutralconditions (pH 1 and 6; 10 μgL –1 Ni,As, Cd, Sb, and Pb; 10 mM NaCl). The carrier solution was 10 mM NaCl.The solutions inside the samplers were measured after 0.5, 1, 3, and6 h equilibrium time.When developing the calibration curvea series of standard solutions, containing 1.0, 2.0, 5.0, 10, 20 μgL –1 Ni, As, Cd, Sb, and Pb at pH 1 and 10 mM NaCl, weremeasured. The carrier solution was 10 mM NaCl. The ICP-MS measurementswere conducted after 24 h of equilibrium time. Nondestructive Measurement of the TemporalElement Profile Changein SWIAn SWI profiler is made of 25 individual samplerswith the assistance of a 3D printer.

The SWI profiler is able to measurethe elements distribution over a distance of 6 cm, with a resolutionof ∼2 mm. To detect the element profile, the SWI profilerswere inserted into paddy soils which have been flooded for half ayear, with 1 cm above SWI and 5 cm buried in paddy soils (C). The porewaterelement concentrations were measured every day under different environmentaldisturbance: Day 0, SWI profiler installation; Day 1, no disturbance;Day 2–3, continuously N 2 bubbling in surface water;Day 4–6, continuously air bubbling in surface water; Day 7–8,continuously N 2 bubbling in surface water. Nitrogen gaswas provided by a high pressure tank, air by an air pump. Three pipetteswere deployed evenly at 1 cm above the SWI in the container, and thebubbling in surface water was via these pipettes. Effectsof Carrier SolutionCarrier solution was usedto expel the solution in the sampling tube.

The composition of carriersolution may affect the diffusion processes of target ions acrossthe membrane during passive sampling stage, and interfere the measurementduring active sample injection stage. It is supposed that carriersolution may modify the characteristics of the membrane. Similarly,a certain ionic strength carrier solution is efficient in reducingthe electrostatic interactions in DET/DGT., As for polyvinylidene fluoride membrane,a complexation effect may occur between metals, like Pb, and fluorideon the membrane. If there is no significantinteraction between target elements and membrane, then oxygen-freeultrapure water is the preferred carrier solution which has minimalinterference to the sampling environment. In this study, three kindsof solutions, including ultrapure water, 10 mM NaNO 3 and10 mM NaCl, were used to drive the sample solution inside the IPIsamplers to ICP-MS.The influences of carrier solution are summarizedin. The results indicated thatthe pH condition did not significantly alter the response of the elementstested. Nickel, As, Cd, and Sb ions showed high permeability throughthe sampler membrane.

High sensitivities of those elements were foundwhen water, NaNO 3, and NaCl solution were used as carriersolution in acidic and near-neutral conditions. However, no Pb signal was observed under near-neutralconditions when using ultrapure water and 10 mM NaNO 3.High sensitivities for Pb ions were observed under acidic conditions,or 10 mM NaCl as the carrier solution under near-neutral conditions.It is speculated that the Pb ions were trapped by the fluorine onpolyvinylidene fluoride membrane by forming fluoride-complexes. Moreover, the blocking effect disappeared whenthere was Cl, which forms Pb complexes which are more stable in solution. Considering the negative influence of fluorineon the measurement of Pb as well as the possible influence on othermetals, fluorine-free membrane, like modified poly(ether sulfone)membrane, maybe a better choice than polyvinylidene fluoride membranefor the quantitatively sampling of metals by IPI samplers.Thecarrier solution effects were further tested in soil conditions.When ultrapure water and 10 mM NaCl were used as the carrier solutionfor soil porewater measurement, a similar phenomenon as in solutionexperiment was observed. No Pb was detected in samples from eithersoils with ultrapure water as the carrier solution ; however, significant Pb was observed in bothsoils with 10 mM NaCl as the carrier solution. To test the samplers’ performance onPb measurement, NaCl solution was chosen as the carrier solution inthis study.The Cl in matrix is known to interfere the detectionof As by forming 40Ar 35Cl +, whichis of the same mass-to-chargeratio of 75As +. In this study, we also noticed an increase of As counting from 800to 2500 , when the carriersolution switched from ultrapure water to 10 mM NaCl.

The detectionlimit gets worse when NaCl solution is used but still acceptable becauseAs concentrations are generally high in As-contaminated soils. Thus,the NaCl solution was used as carrier solution to measure As in solutionand soil porewater samples. Effects of Humic AcidHumic acids are ubiquitous insoil environment, and they may act as natural chelates to complexmetals., The largeHA–metal complex may be rejected by the porewater samplersas a result of their large size., The influences of HA on Ni, As, Cd, Sb, and Pb areshown in.The results indicatedHA treatment had no significant influence on As and Sb at all levels.Unlike As and Sb, Pb measured by the IPI sampler was significantlyreduced by the HA with a concentration of 5–20 mgL –1. Similar phenomena were found on other metals (Ni,Cd). Moreover, HA also extended the equilibration time of Pb, Ni,and Cd from 3 h to 12–24 h with increasing HA. The longer equilibrationtime for metals after adding HA is because HA–metal complexhas much smaller diffusion coefficient than the free metal. Due to the small pores (50 nm) on the IPI sampler,large HA–metal complexes maybe rejected during the sampling.

− Therefore, 24 h equilibration time is recommended for the usingof IPI sampler in soils, especially for the environments containinglarge metal complexes. 1where t is the time (s) thatthe concentration of solute at distance x (cm) canreach equilibration, and D (cm 2 s –1) is the diffusion coefficient of solute.Inthe IPI sampler, x equals the radius of the tube(1 mm), and D is ∼5 × 10 –6 cm 2 s –1 for most metal ions at roomtemperature. Thus, we estimated the equilibrationtime is approximately 17 min. However, the calculated duration may be an underestimate,because the extended ion diffusive pathway through the membrane andother factors are not counted in the calculation.The time-dependent sample loading process was testedin solutioncondition.

As shown in A, all the 5 elements share a similar time-dependent loadingprocess pattern regardless of pH conditions. The elements’concentrations in IPI samplers increased sharply within the firsthour, and then increased slowly to a plateau after 3 h. The equilibriumtime (hour level) in IPI sampler is consistent with the time (hourlevel) yielded in a partial resupply mode of analytes when leavingone side of DET gel to the medium., Therefore,it is concluded that the minimum time required to reach equilibriumof the solute across the IPI membrane is 3 h with HA free medium,but ≥24 h equilibrium time is recommended for the samplingof porewaters. Comparison of sample introductionand IPI sampler based introductionin ICP-MSIPI sampler provides an alternative way to bridgethe environmental samples and analytical machines.

Compared to directsample introduction mode for general ICP-MS analysis, IPI samplerscontain a hollow fiber membrane tube. The tube serves as a passivesampling tube during the sample loading stage and a conduit in activesample injection stage, as described in. On the basis of the working mechanism,we consider the quantitative measurement of the solutes may be influencedby (1) the diffusion of solute from the sampling tube to the silicatube (side diffusion); and (2) solution leakage/exchange during activesample injection stage.Side diffusion might lead the totalamount of solute inside the sampler increasing with deployment time.In the IPI samplers, diffusion suppressors were placed on each sideof the sampling tube to reduce the side diffusion (A).

Calibration Curve and LODThe calibration curve wasgenerated by deploying the IPI samplers in a series of standard solutionsfor 24 h. The response of each element was calculated by the peakareas. The data processing method is shown in. The points higher than baseline +5SD are selectedfor peak area integration. The coefficients of determination for allthe five elements are 0.995. According to IUPAC definition, the LODs are 0.12, 0.67, 0.027, 0.029, and 0.074 μgL –1 for Ni, As, Cd, Sb, and Pb, respectively.

Comparisonof IPI Sampler and Rhizon SamplerThe comparisonof IPI sampler and rhizon sampler for measuring Ni, As, Cd, Sb, andPb was carried out in GZ and QY paddies. Cadmium was below the LOD in both samples.

The two methodsshowed no difference in measuring As and Sb. However, lower Ni andPb were obtained by IPI sampler than rhizon sampler for both soils,which can be explained by the different sampling mechanisms for rhizonsamplers and IPI samplers. Tension-free samplers, like IPI sampler,measure the metal species with the molecular size enabling them topass through the diffusion pores on the sampler freely. In principle,free metals and colloidal metals with the size. Nondestructive Spatial and Temporal MetalMeasurement by SWIProfilerWith developed calibration curves, the SWI profileris able to measure the dynamic changes of element profile in two As-contaminatedpaddy soils. The soils were exposed to different redox conditionsby bubbling air or N 2 gases.

The vertical changes of Asin GZ soil porewater are depicted in. At Day 1, the As concentrations were generallylower than 40 μgL –1 with small variation.The As levels increased slightly with the depth. The deployment ofSWI profiler at Day 0 was probably responsible for the low As concentrationobserved at Day 1 as it may introduce oxygen to soils. Similar Asgradients along SWI were clearly observed in other days.

The resultsrepresented a typical redox controlled element profile, which havebeen widely reported in other studies. Vertical profile changes of soil porewater arsenic (As)along the60 mm SWI in 8 days under different conditions.

The error bars arestandard deviations (SD, n = 3).The temporal changes of As profile in SWI were rarely reported.In this study, we are able to track the daily changes of As profileby using SWI profiler. In GZ soil, the As profile below 10 mm of SWIwas not influenced by the surface water redox condition, but porewaterAs near SWI was sensitive to anoxic–oxic transition (A and ). It increased under anoxic conditions (Day2–3, Day 7–8) and decreased under oxic conditions (Day4–6). The increase of As after pumping N 2 (Day 2–3,Day 7–8) around SWI could be attributed to the release of Asduring metal mineral reduction and dissolution when the redox conditionsat SWI shifted from oxic to anoxic, and from day 4 to 6, the air pumpedinto surface water facilitated Fe oxides formation and As(III) oxidationat SWI, thus As was adsorbed by the oxides and decreased in porewater., However, no obvious As fluctuationwas observed in QY soil.

Theresult reflects a quick matter movement in sandy GZ soil and a relativeslow change in loamy QY soil. This findingstrongly supports the SWI profiler is a powerful and robust tool totrace the temporal change of elements. However, more tests are essentiallyneeded before applying SWI profiler in other environments, like saltyor acidic soils and sediments.

Dynamic vertical profile changes of As(A), Ni (B), Cd (C), Sb(D), and Pb (E) in GZ soils showed in heatmaps. “N”and “O” represent pumping N 2 and air, respectively.The dynamic changes of other elements,including Ni, Cd, Sb, andPb, were also tracked and presented in. The concentrations of those elements were much lower than As. Nickleprofile was constant with time in both soils (B and ). Spatially, porewater Ni concentrations were higher than Ni insurface water in QY soil. The concentrations of Cd in both soils wereas low as.

AThe porewater volume extracted orequivalent porewater volume calculated by the solute diffused intothe samplers was used to evaluate the disturbance of sampling techniquesto soil/sediment environments. The lengths of DET probes, peeper,and SWI profiler are normalized to 5 cm.The sediment porewater sampling techniques mentionedabove havebeen used to reveal the element gradient along SWI., Horizontalinsertion of rhizon samplers can give a good spatial resolution (∼cm)of elements along SWI. However, the samplingzone of rhizon sampler strongly depends on the volume of the retrievedfluids, which may cause bias to the elementprofile. Peeper has a typical resolution of 1 cm, but higher resolution(mm) can be achieved by using small volume chamber.

− The spatialresolution of DET probe is around 2 mm if the gel was cut before ICP-MSmeasurement., The spatial resolution of SWIprofiler is determined by the size of the hollow fiber membrane tube,which has a comparable spatial resolution with high resolution peeper(HR-peeper) and DET probe (mm scale) in this study.SWI profiler has greatadvantages when being applied to the time-dependentelement change in soil porewater. The volume of porewater extractedor equivalent porewater was used to compare the disturbance to soil/sedimentenvironment among different sampling techniques in one sampling event. The calculationprocess was provided in the. Rhizonsampler extracts porewater directly from the soil via a syringe orvacuum vial, the sample volume is depended on the vacuum pressureand sampling time, generally ≥2 mL liquid sample were takenin every sampling event. −, Other samplers work passively, i.e., onlythe dissolved components were extracted, thus the disturbance of passivesamplers is evaluated by the equivalent porewater volume. The removedsolute in porewater by peeper is determined by the designed chambervolume. Low spatial resolution peeper (1 cm) could extract a largeequivalent porewater volume (∼10 mL), but HR-peeper only consumes a small volume of porewater (∼450μL)., By contrast, the least solutein porewater was consumed by DET (440 μL) and SWI profiler (400μL).

The low disturbance of SWIprofiler to porewater makes it an ideal tool to repeatedly sampleporewater at a certain place. Although HR-peeper and DET probe canbe used to study the time series of element change by continuouslydeploying and taking out of HR-peeper or DET probes, the deploymentand take-out cycles may pose disturbances to the sediment, and thecoarse sediment may in turn tear the membrane or gel layer on DETprobes., These influencingfactors may cause high variability to the element profile.

Low mechanicaldisturbance of the sediment can be achieved with rhizon sampler method. However, rhizon sampler would be blocked bythe suspended soil particles under repeated usage., By contrast, SWI profiler has much longer service life, and no blockingevent was noticed after 10 times use in soils.With SWI profiler,it is easy to monitor the high spatial (mm level)distribution of metals at a certain place repeatedly. However, greatcare should be taken to sample porewater from SWI profiler in highfrequency (e.g., daily), since the buffer capacity to porewater isvarying among different soils and sediments.

This indicates, when sampling in high frequency, underestimationof the components in porewater may happen, especially for the soilsor sediments with limited buffer capacity. Therefore, to yield thereliable element profiles, low sampling frequency is recommended forapplying SWI profiler in long-term monitoring.Although allthe samplers’ quality was checked before application,failed samplers were occasionally found in SWI profiler. A diagnosticgraph is shown in to help usersto preview the data and remove invalid data. In this test, no peakswere observed in samples 11and 32, and part of sample 83 peak wasmissing. A postexperiment check found the blocking problem was causedby the dropping debris from carbon fiber caps.The complexityof sample preparation before measurement is a keyparameter when selecting analytical methods. There is almost no costfor sample preparation for SWI profiler method, since the sampleswere directly introduced to ICP-MS.

For rhizon sampler and peepermethods, it is common to use a small amount of acid to stabilize theelement before instrument analysis., The samplepreparation of DET technique is manually intensive. In addition, a 24 h elution with NaOH or HNO 3 is needed for the instrument analysis., In comparison with DET, an advantage for peeper, IPI sampler andrhizon sampler is to obtain clean liquid porewater sample directly,which is almost ready for instrument analysis. Many alternative solutions were proposedto reduce the sample preparation steps for DET probes, e.g., replacingmanually gel slicing with guillotine devices, and coupling DET probe with colorimetric analysis. As for SWI profiler, the sample collection and introductioninto ICP-MS share the same single hollow fiber membrane tube, whichwould greatly simplify the sample preparation and analysis. Pocket tanks download. Typically,it takes only 50 min for the multielement sampling and measurementof the whole samples from one SWI profiler when directly connectingto ICP-MS (2 min/sample × 25 samples/SWI profiler). The highsample measurement throughput is only achievable in “on-line”mode by connecting IPI samplers with ICP-MS. If dirt samples are notallowed in clean lab for ICP-MS operation, then the IPI samplers canwork in “off-line” mode.

The “off-line”mode is time-consuming because soil porewater must be extracted firstand sent for ICP-MS lab with proper preparation.We presentedthe feasibility of coupling SWI profiler with ICP-MS.When the SWI profiler is applied in field, the solution can be pumpedout and stored in tubes for lab-based analysis by the instrumentsable to measurement a small volume of sample (∼100 μL),for examples, ion chromotography (IC), microplate reader, flow cytometer,and dynamic light scattering. − More application based on IPIsamplers can be foreseen in the future and assist the studies on soiland sediment sciences. Supporting Information AvailableThe Supporting Information isavailable free of charge on the at DOI:.Calculation ofthe equivalent porewater extracted bydifferent samplers.