Solid phase extraction of gold(III) on Amberlite XAD-2000 prior to its flame atomic absorption spectrometric determination

A solid phase extraction method for the determination of gold(III) at trace levels by flame atomic absorption spectrometer (FAAS) was developed. The method was based on retention of gold as chloro complexes through the Amberlite XAD-2000. The effect of some analytical parameters including hydrochloric acid concentration, sample volume, sample and eluent flow rates, eluent volume, eluent concentration and interfering ions on the recovery of gold(III) was investigated. The retention of gold(III) from 1.5 mol l⁻¹ HCl solution and the recovery of gold with 0.07 mol l⁻¹ NH₃ solution were quantitative (≥95%). The relative standard deviation (RSD) was calculated as 3.2% (n = 10). The detection limit for gold was 2 μg l⁻¹. The accuracy was checked with the determination of gold spiked an artificial seawater and a pure copper samples.     

Adsorption and removal of oxo-anions of arsenic and selenium on the zirconium(IV) loaded polymer resin functionalized with diethylenetriamine-N,N,N',N'-polyacetic acid

A polymer adsorbent in which a Zr(IV)-edta complex analogue is immobilized has been prepared and applied to the removal of oxo-anions of As(III), As(V) and Se(IV). Effective retention of these anions has been demonstrated with the proposed polymer complex system. The adsorption mechanism of oxo-anions onto the Zr(IV)-chelated polymer complex has been investigated using Zr(IV)-edta as the model compound. The formation of mixed complexes with oxo-anions has been exemplified by the isolation of the carbonato complex K2[Zr(CO3)edta].3H2O, the structure of which has been confirmed by X-ray crystallography. NMR study suggests that oxo-anions that form weak or moderate conjugate acids, including those of As(III), As(V) and Se(IV), can form mixed complexes with Zr(IV)-edta using the unsaturated coordination site. However, oxo-anions of strong conjugate acids did not show any appreciable interaction with this complex. According to these observations, retention of oxo-anions on the Zr(IV)-chelated polymer complex has been interpreted by a ligand substitution reaction. The adsorption characteristics of As(III), As(V) and Se(IV) on the Zr(IV)-loaded resin have been examined with respect to the equilibrium adsorption, percentage extraction and the effect of co-existing ions. The adsorption and desorption cycles of the oxo-anions have been demonstrated using a column packed with the proposed resin without any loss of column performance, which indicates the possibility for repeated use.     

Effects of pH and low molecular weight organic acids on competitive adsorption and desorption of cadmium and lead in paddy soils

The bioavailability and ultimate fate of heavy metals in the environment are controlled by adsorption-desorption process. Batch equilibrium experiments were performed to assess the effects of pH and low molecular weight organic acids (LMWOAs) on competitive adsorption and desorption of cadmium and lead in paddy soils from China. The results indicated that both soils exhibited greater sorption capacity for lead (Pb) (1.37-1.61-fold) than cadmium (Cd) as estimated by the maximum sorption parameter (Q) from the Langmuir equation. The Langmuir bonding energy coefficient (b) and distribution coefficient (K (d)) were greater for Pb than for Cd, furthermore, b (binary) and K (d) (single) were greater than b (single) and K (d binary), indicating that competition for sorption sites promote the retention of both metals on more specific sorption sites. Both Cd and Pb desorption as a function of solution pH was characteristic of "S" pattern. The presence of LMWOAs inhibited Cd or Pb desorption at the low concentrations (≤0.1 mmol L(-1)) but promoted Cd and Pb desorption at higher concentrations (≥0.5 mmol L(-1) for citric acid and ≥1 mmol L(-1) for malic and oxalic acid). The two paddy soils had a greater d (Cd) than d (Pb) in the presence of LMWOAs, indicating that Cd desorption was more affected by the presence of LMWOAs in binary metal system.     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Multiple kinetic Langmuir modeling to predict the environmental behaviour of As(v) in soils

A soil with a relatively high Fe content (2.82% [w/w]) was loaded for up to one year with As(v) by equilibrating it with a solution containing 1000 mg l(-1) As(v) at a soil mass-to-solution ratio of 0.1 kg l(-1). The incorporation of As(v) into the soil and its distribution over the soil phases were monitored by sampling at strategic time intervals using an operationally defined five-step sequential extraction procedure (Wenzel et al., Anal. Chim. Acta, 2001, 436, 309) and subsequent As measurement. A multiple kinetic Langmuir model was developed to retrieve the dynamic parameters (adsorption and desorption rate constants, capacities and Langmuir equilibrium constants) for each of the soil phases by numerical fitting of the experimental adsorption data to the model. Under the equilibration conditions used the adsorption rate constants for all five operationally defined soil phases were very similar but the desorption rate constants decreased by a factor of ca. 150 from soil phase 1 (non-specifically sorbed As) to 5 (residual phases). This implies that As(v) incorporation "deeper" into the soil leads to stronger binding which is associated with the Langmuir equilibrium constants (adsorption rate constants/desorption rate constants). Equilibration of the soil with As(v) was complete in ca. 10 days with As(v) predominantly bound to soil phase 2 (specifically sorbed As) and soil phase 3 (amorphous and poorly crystalline hydrous oxides). X-Ray absorption spectroscopy techniques revealed that these binding characteristics may be related to adsorption of As(v) on Si- and/or Al-containing structures and natural hydrous iron oxide (HFO) surface sites, respectively. Since the model is independent of the initial As(v) concentration in the solution and the soil mass-to-solution ratio, the behaviour of the thus characterized soil-As(v) system can be predicted for a range of conditions. Simulations showed that in an accidental As(v) spill the soil studied would actively scavenge As(v) by instantaneous adsorption onto all soil phases followed by redistribution of As(v) from weaker binding sites to stronger ones over time.     

Oxidation of Cr(III) to Cr(VI) during chlorination of drinking water

Drinking water treatment typically uses strong oxidants such as chlorine which are capable of converting Cr(III) to Cr(VI). The rates and extent of Cr(III) oxidation by chlorine are not well established. Cr(III) oxidation experiments were therefore conducted in distilled deionized water and New York City tap water dosed initially with Cr(III) and supplemented with sodium hypochlorite to increase free chlorine residual. Reaction progress was monitored using capillary electrophoresis which quenched reactions and allowed for quantification of Cr(VI). Three different forms of Cr(III) were used as reactants: a Cr(III) nitrate salt, Cr(III)-EDTA, and Cr(III) hydroxide. Rates of Cr(VI) production for all three forms of Cr(III) were rapid, on the order of hours. However, oxidation rates slowed and a plateau in Cr(VI) concentrations was reached. This resulted in less than 100% conversion of Cr(III) to Cr(VI) even at relatively high chlorine doses (10 to 100 mg L(-1) as Cl(2)). The loss of free chlorine due to a non-Cr chlorine demand, the precipitation of Cr(III) to Cr(OH)(3)(s), and the partial oxidation of Cr(III) to intermediate oxidation states (i.e. Cr(IV) and Cr(V)) were examined and eliminated as possible explanations for this behavior. Consumption of chlorine via reaction with intermediate oxidation states of Cr is therefore offered as a possible explanation for the plateau in Cr(VI) concentrations.     

Novel solid-phase extractor based on functionalization of multi-walled carbon nano tubes with 5-aminosalicylic acid for preconcentration of Pb(II) in water samples prior to determination by ICP-OES

New solid-phase extractor (MWCNTs-5-ASA) was synthesized via covalent immobilization of 5-aminsalicylic acid onto multi-walled carbon nanotubes (MWCNs). The success of the functionalization process was confirmed using Fourier transform infrared spectroscopy, scanning electron microscope, and surface coverage determination. Batch experiments were conducted as a function of pH to explore MWCNTs-5-ASA efficiency to extract several metal ions viz., Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II). It was found that Pb(II) exhibits the highest extraction percentage with maximum adsorption capacity 32.75 mg g^?1. Its binding performance was well fitted with Langmuir sorption isotherm. On the other hand, the selective separation and preconcentration of trace Pb(II) under dynamic conditions prior to determination by inductively coupled plasma-optical emission spectrometry was investigated under different parameters. These included the rate of flow and volume of sample solution, in addition to the type of the eluate, its volume and concentration. The effect of a variety of foreign ions on the recovery percentage was also evaluated. Trace Pb(II) ions present in 500 mL aqueous solution adjusted to pH 4.0 were retained on 50 mg of MWCNTs-5-ASA and completely eluted using 4.0 mL of 2 M HNO₃. The limit of detection and the precision of the method were 0.25 ng mL^?1 and 2.8 %, respectively (N?=?5). This methodology has been applied for the determination of Pb(II) in water samples with good results.     

气相色谱-质谱法测定大气中98种挥发性有机物

通过色谱-质谱联用法(简称GC-MS),利用低温冷阱技术对大气中的VOCs进行浓缩富集,然后经过加热解吸分别至毛细管色谱柱和FID检测器及MS检测器,对大气中98种挥发性有机化合物(VOCs)进行分离、定性、定量测定。方法检出限为0.008×10-9~0.100×10-9(V/V);线性相关系数的平方值为0.992 7~1,相对标准偏差为4.0%~20.2%,总体标准偏差为0.154 2~0.952 1。     

Ultrasound-assisted ionic liquid-based microextraction combined with least squares support vector machines regression for the simultaneous determination of aluminum,gallium, and indium in water and coal samples

A new simple and rapid ultrasound-assisted ionic liquid-based microextraction method was applied to preconcentrate aluminum(III), gallium(III), and indium(III) ions from water samples as a prior step to their simultaneous spectrophotometric determination using least squares support vector machines regression. In the novel procedure, 1-hexyl-3-methylimidazolium hexafluorophosphate [C₆MIM][PF₆] was dispersed into the aqueous sample solution as fine droplets by ultrasonication, and the analytes were extracted into the ionic liquid phase after complexation with 1,2,5,8-tetrahydroxy anthraquinone (quinalizarine). After centrifuging, the fine droplets of extractant phase were settled to the bottom of the conical-bottom glass centrifuge tube. The detection limits for Al(III), Ga(III), and In(III) were 1.70, 2.02, and 2.06 ng mL⁻¹, respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of ten replicates, was below 3.2% for all elements. The method was successfully applied for the determination of Al(III), Ga(III), and In(III) in real samples.     

Solid phase extraction of gold(III) on silica gel modified with benzoylthiourea prior to its determination by flame atomic absorption spectrometry

A new method has been developed for the determination of gold based on separation and preconcentration using silica gel modified with benzoylthiourea. The optimum experimental parameters for preconcentration of gold, such as acid concentration, sample flow rate, eluent and matrix ions, have been investigated. Gold could be quantitatively retained in the 0.25-2.0 mol L(-1) HCl and HNO(3) concentrations, and then eluted completely with 0.5 mol L(-1) thiourea in 1.0 mol L(-1) HCl. The sorption capacity of gold(III) is 0.92 +/- 0.04 mmol g(-1) with a high enrichment factor of 267. The relative standard deviation of the method, RSD%, was found as 1.2% for 0.1 microg mL(-1). The detection limit for gold was 1.4 microg L(-1). The validation of the proposed method was checked by the analysis of certified reference soil materials. The presented procedure was applied to the determination of gold in some environmental samples.     

Tuning the surfaces of palladium nanoparticles for the catalytic conversion of Cr(VI) to Cr(III)

This work reports the feasibility of using Pd nanoparticles as innovative catalysts in the conversion of reducible contaminants from toxic to benign forms. Cr(VI) is a known carcinogen while the trivalent chromium salts are believed to be non-toxic. The ability of Pd nanoparticles to catalyze the rapid reduction of Cr(VI) to Cr(III) using reactive sulfur intermediates produced in situ was therefore studied. Using a microchamber set at 130 degrees C, the reduction mixture consists of palladium nanoparticles and sulfur (PdNPs/S), which generated highly reducing sulfur intermediates that effected the reduction of Cr(VI) to Cr(III) by 1st order reaction kinetics. UV-visible spectroscopy and cyclic voltammetry were employed to monitor the reduction process. The results showed that 99.8% of 400 microM Cr(VI) was reduced to Cr(III) by PdNPs/S in one hour compared to 2.1% by a control experiment consisting of sulfur only. The rate of Cr(VI) reduction was found to be dependent on temperature and pH and was greatly enhanced by the addition of PdNPs. Subsequent application of this approach in the reduction of Cr(VI) in soil and aqueous media was conducted. In contrast to the control experiments with and without PdNPs or sulfur, greater than 92% conversion rate was obtained in the presence of PdNPs/S within 1 hour. This represents over a 500-fold improvement in conversion rate compared to current microbial approaches. XPS analysis provided the confirmation regarding the oxidation states of Cr(VI), Cr(III) and the nature of the reactive intermediates. This work offers PdNPs/S as a new interface for the reduction of high oxidation state heavy metal pollutants.     

On-site simultaneous determination of anions and cations in drainage water using a flow injection-capillary electrophoresis system with contactless conductivity detection

Drainage water diverted from a farm pasture, which was heavily loaded with manure, was monitored during a rain event. Concurrent anion and cation determinations at intervals of 10 min could be achieved with a new capillary electrophoresis system employing dual injection at opposite ends of the separation capillary. The flow injection approach enabled automation of the sampling process. Interruption of the separation voltage was not necessary. Contactless conductivity detection with an electrolyte solution optimized for the purpose allowed the facile simultaneous detection of the inorganic ions Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), NO(2)(-), NH(4)(+), K(+), Ca(2+), Na(+) and Mg(2+) and the acquisition of temporal concentration profiles of these species. The detection limits achieved were between 20 and 200 [micro sign]g l(-1) for all ions and the repeatability of peak areas and peak heights was better than 1%. The quantitative results were verified by analysing individual samples later in the laboratory with photometry and ion chromatography and the average deviations were found to be between 4 and 12%. This contribution presents a further step in the development of capillary electrophoresis towards a fully automated, low maintenance field method.     

水中丙烯酰胺气相色谱测定方法研究

研究建立了大口径毛细管柱气相色谱法测定水中丙烯酰胺的方法。优化了水中丙烯酰胺的衍生化条件,用乙酸乙酯和正己烷混合溶剂萃取衍生产物,萃取后直接进行色谱分离分析,水中丙烯酰胺的最低检测浓度为0.05μg/L,回收率在94.5%～113%之间;进行6次平行精密度试验,相对标准偏差低于11.5%。研究建立的气相色谱法简便、快速、准确、重现性好,定量、定性准确可靠,适合水中丙烯酰胺的分析测定。     

Desorption Kinetics of Benzene in a Sandy Soil in the Presence of Powdered Activated Carbon

Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption–desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q _irr) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption–desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q _irr) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4–40 times) rate constant for rapid process (k ₁) than that for slow process (k ₂), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.     

Chromium speciation in a contaminated groundwater: redox processes and temporal variability

Chromium species (Cr(III), Cr(VI), and Cr(III)-organic) in groundwater of a tannery contaminated area were monitored during pre- and post-monsoon seasons for a period of 3 years (May 2004 to January 2007). The objectives of the study were (1) to investigate the temporal variation of chromium species and other matrix constituents and (2) to study the redox processes associated with the temporal variation of chromium species. Samples were collected from 15 dug wells and analyzed for chromium species and other constituents. The results showed that the groundwater was relatively more oxidizing during post-monsoon periods than the pre-monsoon periods. Except one sample, the concentration of chromium species were found in the order of Cr(VI)>Cr(III)>Cr(III)-organic complexes during all the pre- and post-monsoon periods. In most of the wells, the concentrations of Cr(III), Cr(VI), and Cr(III)-organic decreased during post-monsoon periods compared to their pre-monsoon concentrations. However, the Cr(VI)/Cr_Total ratio still increased and the Cr(III)/Cr_Total ratio decreased during post-monsoon periods in most of the samples. The possible mechanisms for the temporal variation of chromium species were (1) Fe(II) reduction of Cr(VI) vs oxidation of Fe(II) by dissolved oxygen and (2) oxidation of Cr(III) by Mn(IV).     

Speciation and quantification of Hg in sediments contaminated by artisanal gold mining in the Gualaxo do Norte River,Minas Gerais,SE, Brazil

The Iron Quadrangle in SE Brazil was, in the eighteenth century, one of the most important Au producing regions of Brazil. In this region, gold is produced, even today, by artisanal methods that use Hg to increase the extraction efficiency with no control of Hg release to water systems and the atmosphere. In this context, the Gualaxo do Norte River is of particular interest; its springs are located in the Doce River basin, an important Brazilian basin that supplies water for 3.5 million people. The main goal of this work was to quantify and speciate the Hg in the sediments of the Gualaxo do Norte River using a direct mercury analyzer and gas chromatography-pyrolysis-atomic fluorescence detection system. Statistical analyses consisted of principal component analysis, aiming to assess interactions among elements and species and to group the variables in factors affecting the properties of sediment. The results show that total Hg (THg) and methylmercury (CH₃Hg⁺) concentrations in samples ranged from 209 to 1207 μg kg^?1 and from 0.07 to 1.00 μg kg^?1, respectively (methylation percentages from 0.01 to 0.27%). Thermal desorption analysis showed that mercury is mainly present in the oxidized form, and correlation analyses pointed to a relationship between THg and MnO, indicating that manganese can oxidize and/or adsorb Hg. Together, MO and CH₃Hg⁺ are important parameters in the third principal component, indicating the influence of OM on the methylation process. This first investigation on Hg methylation in this small-scale gold mining area points to the possibility of Hg bioaccumulation and to the need of better understanding the biogeochemical cycle of Hg in this area. Samples were collected in 2012, prior to the 2015 Fundão Dam disaster. The results are also a record of the characteristics of the sediment prior to that event.     

Geochemical assessment of metal transport in glacial till during electrokinetic remediation

This paper presents the chemical speciation and retention behavior of chromium (Cr), nickel (Ni), and cadmium (Cd) prior to and after the electrokinetic remediation in glacial till soil. The speciation of the metals was predicted using the chemical speciation program MINEQL⁺. The simulations were performed for single-contaminant with only Cr(VI) or Ni, and multi-contaminants consisting of: (1) Cr(VI), Ni, and Cd; (2) Cr(III), Ni and Cd; (3) Cr(VI), Cr(III), Ni and Cd; (4) Cr(VI), Ni, and Cd with reducing agents; and (5) Cr(III), Ni, and Cd with oxidizing agent (Mn). The results showed that the speciation and distribution of cationic metals [Ni, Cd, and Cr(III)] in glacial till soil remain unaffected or slightly affected during electrokinetics. This is attributed to the high pH buffering capacity of the glacial till, leading the metals to precipitate in the soil prior to and after electrokinetics. This study showed that during electrokinetics, Cr(VI) existed as anionic complex and migrated towards the anode and the migration is maximum in case of a single-contaminant system. The study also showed that near the anode in the absence of any reducing and oxidizing agent, Cr(VI) mostly adsorbed, and some of Cr(VI) reduced to Cr(III) and migrated towards the cathode and finally precipitated due to high pH conditions. Ni and Cd remain adsorbed or precipitated due to the high pH conditions throughout the soil. Among the reducing agents, the sulfide had significant effect on the migration of metals compared to ferrous ions. While in the presence of oxidizing agent (Mn), no noticeable Cr(VI) was found in the soil sample indicating the reduction of Cr(VI) to Cr(III) and the predominance of reducing conditions due to the presence of naturally occurring iron in the glacial till soil. Overall, this study provides a reasonable explanation of the speciation and distribution of chromium, nickel and cadmium during the electrokinetic remediation of glacial till soil.     

Spectrophotometric determination of ferbam (iron(III) dimethyldithiocarbamate) in commercial sample and wheat grains using 4,7-diphenyl-1,10-phenanthroline after extraction into mesityl oxide

A procedure has been developed for the determination of iron(III) dimethyldithiocarbamate by converting it into iron(II)-bathophenanthroline complex, which is then extracted into mesityl oxide in the presence of potassium perchlorate. The absorbance is then measured at 534 nm against a reagent blank. Beer's law is obeyed over the concentration range 0.5-20 microg ml(-1) in the final solution. The method is sensitive, highly selective and can be used for the determination of ferbam in a commercial sample, and in mixtures with various dithiocarbamates (ziram, zineb, maneb, etc.) and in wheat grains.     

Is PM10 mass measurement a reliable index for air quality assessment? An environmental study in a geographical area of north-eastern Italy

The aim of this study was to measure the concentration of some metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Ti) in PM(10) samples collected in one urban and one industrial site and to assess that PM(10) total mass measurement may be not sufficient as air quality index due to its complex composition. Metals were determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and differential pulsed anodic stripping voltammetry (DPASV). The measured concentrations were used to calculate the content of metals in the PM(10) total mass, and to estimate the enrichment factors and the correlations between PM(10), metal concentrations and meteorological data for the two sites. The mean PM10 concentration during the sampling period in the urban site exceeded the annual European Union (EU) standard (40 microg/m(3)) and, for some sampling days, the daily EU standard (50 microg/m(3)) was also exceeded. In opposite, both EU standards were never exceeded in the industrial site. The overall metal content was nearly double in the industrial site compared to the urban one, and the mean Ni concentration exceeded the EU annual limit value (10 ng/m(3)). The metals with the highest enrichment factor were Cd, Cu, Ni and Pb for both sites, suggesting a dominant anthropogenic source for these metals. Metal concentrations were very low and typical of rural background during Christmas holidays, when factories were closed. PM(10) total mass measurement is not a sufficient air quality index since the metal content of PM(10) is not related to its total mass, especially in sites with industrial activities. This measurement should be associated with the analysis of toxic metals.     

Human K10 epithelial keratin is the most abundant protein in airborne dust of both occupied and unoccupied school rooms

Previously it was demonstrated that the levels of large particles (>2 micron) and associated bacterial cell envelope markers increase greatly on occupation in schools; it was hypothesized that the source of both was shed human skin. In the current work to test this hypothesis, room air cleaners were used to collect airborne dust (>50-100 mg) from occupied and unoccupied school rooms which was then subjected to proteomic analysis. Proteins were extracted from the dust and separated using two dimensional gel electrophoresis (2D GE). In situ digestion of protein spots with trypsin released peptides, which were subsequently analyzed by matrix assisted laser desorption/deionization, time-of-flight mass spectrometry (MALDI-TOF-MS) and tandem mass spectrometry (MALDI-TOF-MS-MS). In Coomassie blue stained gels, a single spot generally dominated the 2D gels; this protein was identified by tandem mass spectrometry as K10 epithelial keratin. The results experimentally confirm previous anecdotal reports that human skin is readily shed into air and suggest that increased levels of microbial markers and large particles observed in occupied rooms are also derived from skin.