Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from catalytic and thermal oxidizers burning dilute chlorinated vapors

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins) have been found from 57 field tests on the oxidation of low (a few to a few hundred) parts per million levels of chlorinated and non-chlorinated volatile organic compounds (VOCs). The oxidation occurs in catalytic oxidizers with platinum, platinum/palladium or chromium(IV) oxide combustion catalysts, or in thermal oxidizers (without a catalyst). The catalyst inlet temperatures ranged from 293 to 573 degrees C. The thermal oxidizer operating temperatures (post-flame) were from 773 to 927 degrees C. Data of the toxic dioxin and furan isomers are reported and also weighted and expressed as international toxic equivalents (TEQ) of 2,3,7,8-tetrachlorodibenzo-p-dioxin. The maximum stack emissions, 1.07 ng/m3 TEQ, occurred at 293 degrees C. Salient results of this field study are: (1) TEQ levels in the stack exponentially increase with a decrease in operating temperature, an empirical equation is TEQ (ng/dscm)=8.4 exp(-0.0084T degrees C); (2) dioxin/furan production occurs at the combustion catalyst; (3) small variations in temperature cause large changes in the congener distribution of the dioxin and furan isomers; (4) molar TEQ yields from the parent compounds fed to the oxidizers are very small (10(-9)-10(-13)); (5) catalytic and thermal oxidizers may destroy dioxins fed from the ambient air; and (6) the oxidation of chlorinated VOCs with non-chlorinated VOCs reduces emissions of dioxins, likely due to the consumption of Cl in producing HCl. Laboratory investigations are needed to understand how dioxins are formed (and emitted) under conditions of this study.     

Multi-component behavior of fixed-bed adsorption of dioxins by activated carbon fiber

The multi-component behavior of fixed-bed adsorption of dioxins (DXNs) was examined through detailed analyses of the concentration profiles of isomers in fixed-bed activated carbon fiber (ACF). Regularities in both adsorption rates and strengths were clarified. (1) The rate of transfer in the adsorption of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCCDs/DFs) tends to increase with decreasing number of chlorine substituents. Axial dispersion also tends to increase with a decreasing number of chlorine substituents under our experimental conditions. (2) Homologues with the same number of chlorine substituents in PCDDs/DFs have similar adsorption strengths. The adsorption strength of PCDD/DF isomers is probably greater than that of co-planar polychlorinated biphenyls (co-PCB) isomers when the number of chlorine substituents is identical. (3) The adsorption strength of isomers depends on their molecular structure. In PCDDs/DFs the toxic isomers, all of which have vicinal chlorine substituents at the 2, 3, 7 and 8 positions, are relatively strong. It is clear, especially in TeCDDs, that isomers with vicinal chlorine substituents are stronger than isomers without. In co-PCBs, isomers without chlorine substituents at ortho positions are stronger than those with, and (4) A close analogy exists between the adsorption strength order for ACF and the elution order in gas chromatography (GC).     

Retention time profiling of all 136 tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans on a variety of Si-Arylene gas chromatographic stationary phases

The applicability of three different Silphenylene Silicone co-polymer (Si-Arylene) GC stationary phases (J&W Scientific DB-5ms, Varian VF-5ms, and VF-Xms) has been evaluated for the separation of all 136 tetra- through the octa- chlorinated dibenzo-p-dioxins (PCDD) and chlorinated dibenzofurans (PCDF) from closely eluting isomers using gas chromatography/high resolution mass spectrometry (GC/HRMS). Their relative performance data are compared to the “conventional” 5% diphenyl 95% dimethylpolysiloxane GC column (Supelco Equity-5) and to each other based on absolute retention times, visualized mass chromatograms, and the separation of 2,3,7,8-substituted isomers. VF-Xms GC column was able to demonstrate a better performance towards separation of 2,3,7,8-substituted PCDD/PCDF compared to other Si-Arylene GC columns tested, where only 2,3,4,7,8-PnCDF can not be resolved from 1,2,3,6,9-PnCDF and 2,3,4,6,7,8-/1,2,3,6,8,9-HxCDF and 1,2,3,7,8,9-/1,2,3,4,8,9-HxCDF can be at least partially resolved. These data suggest that the development of a single GC column for the separation of all 17 2,3,7,8-substituted dioxins and furans is feasible, which therefore could be used as a standard tool for the PCDD/PCDF methods globally including USEPA methods 1613b, 8290A, 8280B, European Standard Method EN 1948, Canadian methods DFPCB-E3418, EPS 1/RM/19, Japanese methods JIS K0311 and JIS K0312. Having one specific GC column to separate all 2,3,7,8-substituted PCDD/PCDF will significantly improve the data quality, comparability by the various methods and assessment techniques while simultaneously leading to a more cost and time efficient operation.     

Emission and chlorination pattern of PCDD/PCDF predicted from indicator parameters

The emission and chlorination pattern of polychlorinated dioxins and dibenzofurans from waste combustion shows a close covariation with that of chlorinated benzenes and phenols. This covariation can be utilized to predict the emission levels of specific isomers as well as the pattern of congeners.     

Evidence of natural organochlorine formation in peat bogs

Peat samples from four ombrotrophic and two minerotrophic peat bogs in New Brunswick, Canada, have been analyzed for polychlorinated dioxins and furans (PCDD/DF's) as well as other organochlorine compounds. Data from each bog show occasional low levels of 2,3,7,8-substituted tetra-through octachloro dioxins and furans. Mono-through trichlorodioxins and furans have also been identified.

A consistent pattern was observed among the TCDD's and TCDF's which was reproducible across all peat samples analyzed. A single TCDF isomer (2468-TCDF) predominates over all other isomers whereas two isomers of TCDD were prominent (1,3,6,8-TCDD and 1,3,7,9-TCDD). This distinct isomer pattern is present at all depths and is different from that of atmospheric deposition or known sources of PCDD/DF's (eg. fly ash, pulp and paper effluent etc). The pattern is replicated with in vitro oxidative coupling of 2,4-dichlorophenol at pH 2.9 using a commercially available chloroperoxidase from the fungus Caldariomyces fumago.

Significant incorporation of ³⁶Cl-occurred in peat. Autoclaving decreased incorporation while adding casein hydrolysate increased it. The incorporation mirrored the metabolic activity (CO₂ production) of samples consistent with organochlorine synthesis being due to biological activity.

Total Organic Halide (TOX) levels in peat show a wide range in values reaching ca. 1000 ppm at mid-depth in the ombrotrophic Kelly's Bog. TOX in Kelly's Bog occurs at all depths and, since the topography probably excludes leaching from surrounding areas, a local origin of organochlorines is suggested.

Chloroform and a range of chlorinated aromatic compounds (chlorophenols, chlorophenoxy and chlorobenzoic acid derivatives) have also been identified in peat.

Our findings to date are consistent with hypothesis for a biogenic origin for at least some of the organochlorine compounds, including some of the PCDD/DF's, found in peat bogs.     

Dependence of GC-RRTs on the solvent-accessible surface area of dioxins and related compounds

The correlation between gas chromatograph relative retention times (GC-RRTs) of dioxins and related compounds, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated naphthalenes (PCNs), and their solvent-accessible surface area (SAS) was analyzed for congeners and isomers. GC-RRTs were linearly dependent on SAS for congeners while there was little dependence for isomers. However, by using classification parameters, Nad-Cl, Nad-H, N1,9Cl, and NalphaCl, based on the substitution positions and patterns of chlorine and/or hydrogen atoms bound to the molecular skeleton, a linear relationship was found among isomers. Furthermore, the GC-RRTs of CDD, CDF, and CN isomers, which are planar, decreased despite increasing SAS, and this tendency was enhanced with the above classification. The retention behavior was explained in terms of the effective enhancement of molecular hydrophobicity caused by an increase in the number of adjacent chlorine pairs.     

Dispersion modelling of dioxin releases from the waste incinerator at Avonmouth,Bristol, UK

A modified Gaussian atmospheric dispersion model, Industrial Source Complex (ISCST3), is used to estimate toxic equivalent ground level concentrations (GLC) of dioxins emitted from the Avonmouth municipal waste incinerator (MWI) in Bristol, UK. The sensitivity of the predicted GLC to various vapour and particle partitioning scenarios is reported. Predictions incorporating local terrain and actual emission data are used to estimate the mean incremental intake of dioxin due to MWI operation for local residents, through an existing multi-pathway human exposure model. Results are compared with predictions of incremental intake for a generalised MWI. The mean incremental dioxin intake for a hypothetical maximum exposed individual (HMEI) is shown to be up to 46.5% of the background intake compared to only 1.14% for the generalised MWI scenario. This indicates that the use of local terrain and emission data in MWI dispersion modelling is crucial for health risk assessments associated with human dioxin intake, especially in view of the current debate over the tolerable daily intake for dioxins.     

Enhancement in fecal excretion of dioxin isomer in mice by several dietary fibers

The effect of increased nutrients (protein, lipid, vitamins and minerals) on dioxin-induced toxic manifestations such as immune suppression, hepatic hypertrophy, splenic atrophy and enzyme induction was investigated in mice after oral administration of 1,2,3,4,7,8-HxCDD (HxCDD) as one of a representative compound of dioxin isomers. Consequently, it appeared that increased minerals and vitamins in the diet prevented immune suppression by HxCDD. In addition, to clarify the additive effect of nutrients and the ability to hasten the excretion of dioxins by dietary fiber, the adsorbing of dioxins by 16 dietary fibers was investigated by in vitro experiment. Among 16 dietary fibers, locust bean gum, pectin, alginic acid, guar gum, chitin and cellulose were effective in binding dioxin isomers. These dietary fibers also enhanced the fecal excretion of HxCDD in mice.     

Human milk survey for dioxins in the general population in Japan

BACKGROUND: Much attention has been paid to the level of dioxins in breast milk in Japan but few large-scale studies have been conducted on the subject. METHODS: From 1997 to 2002, we collected 839 samples of breast milk from primiparas residing throughout Japan. Starting in 1999, breast milk was also collected from secundiparas. Seven isomers of polychlorinated dibenzo-p-dioxins (PCDDs), 10 of polychlorinated dibenzofurans (PCDFs), 4 of coplanar polychlorinated biphenyls (Co-PCBs) and 8 of mono-orthochlorinated polychlorinated biphenyls (mono-ortho PCBs) were analyzed by employing gas chromatography and mass spectrometry. A correlation between the level of dioxins in human milk and the age of the mothers was noted for the primiparas and the secundiparas; and the levels were compared between the first and the second deliveries. Grouped by parity and prefecture in each year, observations were also made on the trends in these levels. Dioxin levels are shown by using geometric means because their distributions were skewed to the left. RESULTS: The sum of PCDDs and PCDFs, Co-PCBs, mono-ortho PCBs, and total dioxins in the breast milk of primiparas were 13.9, 5.4, 3.4, and 22.7 pg TEQ/g fat, respectively. In the samples obtained from secundiparas, these levels were 63-68 percents of those taken from the primiparas. The correlation coefficients between the PCDDs/DFs, Co-PCBs, mono-ortho PCBs, and total dioxins and the age of the primiparas were 0.19, 0.17, 0.36, and 0.24, respectively. All these correlations were statistically significant (p < 0.001). The positive correlations between these contaminants and the age of the secundiparas were also examined. The total dioxins as well as PCDDs/DFs, Co-PCBs, and mono-ortho PCBs in the breast milk of the primiparas declined significantly between 1998 and 2002 (regression coefficients: -0.04, -0.05, -0.03, and -0.03, respectively). However, no significant decline in these levels was observed when sorted by prefectures. CONCLUSIONS: Much attention should be paid to the age and parity of nursing mothers when investigating the relationship between the level of dioxins in breast milk and the body burden of infants.     

The role of metals in dioxin formation from combustion of newspapers and polyvinyl chloride in an incinerator

Newspapers impregnated with NaCl mixed with various chloride metals (CuCl2, MgCl2, MnCl2, FeCl3, NiCl2, and CoCl2) and electric wire coated with polyvinyl chloride (PVC) were combusted in a well-controlled incinerator. Exhaust gas samples collected at the outlet of the incinerator were analyzed for dioxins (PCDDs, PCDFs, and coplanar PCBs) by gas chromatography/mass spectrometry. The amount of total dioxins formed from newspaper samples ranged from 34.2 ng/g (with NaCl+CoCl2) to 67.0 ng/g (with NaCl+CuCl2). PCDFs composed 88-94% of the total dioxins formed in the exhaust gases. The highest levels of PCDF isomers obtained were Cl3-CDF from the sample with NaCl+CuCl2 (14.8 ng/g), Cl2-CDF from the sample with NaCl+MgCl2 (12.3 ng/g), and Cl(1)-CDF from samples with NaCl+MnCl2 (12.6 ng/g), with NaCl+FeCl3 (11.8 ng/g), and with NaCl+NiCl2 (13.3 ng/g), and with NaCl+CoCl2 (8.62 ng/g). The total of Cl4-8-CDDs comprised 76-88% of the total Cl1-8-CDDs. In particular, Cl7-CDDs had the highest levels except for the sample with NaCl+NiCl2. Total dioxins formed from samples of electric wire coated with PVC and PVC alone were 38.3 ng/g and 112 ng/g, respectively, suggesting that the presence of copper reduced dioxin formation.     

Bio-availability of PCDDs and PCDFs on fly ash after semi-chronic oral ingestion by the rat

Groups of rats (n = 5) were fed a diet containing 2.5% RCl pre-treated fly ash from the electrostatic precipator of a municipal incinerator during 34, 59 and 99 days. Livers were analysed for 2,3,4,7,8-pentachlorodibensofuran and higher chlorinated dibenso(p)dioxins (PCDDs) and dibensofurans (PCDFs). All isomers retained in the liver had a 2,3,7,8-chlorine substitution pattern. Total group dose varied between 0.2 and is μg for each individual retained compound. Retention in the liver was highest for 2,3,4,7,8-PnCDF, being 14% of the dose for the group killod on day 99. The other isomers detected in the livers had a retention generally below 10%. The 2,3,7,8-substituted hexa- and hepta- chlorinated PCDDs and PCDFs were retained in the liver in constant relative concentrations throughout the experiment, which closely approached a linear relationship to the administered dose.     

Formation of dioxins from combustion of polyvinylidene chloride in a well-controlled incinerator

Polyvinylidene chloride (PVDC; polymer of 1,1-dichloroethylene) was combusted with paper in a well-controlled, small-scale incinerator at an average grate temperature of 700 °C, and then dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases were analyzed by gas chromatography/mass spectrometry. PVDC lowered the combustion temperature due to its less flammable character. The amount of total dioxins (PCDDs + PCDFs + coplanar-PCBs) formed in the exhaust gas was 58.0 ng/g of a combustion sample and its toxicity equivalency quantity (TEQ) value was 0.64 ng-TEQ/g. The amount of PCDDs formed in the sample ranged from 2.33 ng/g (Cl₈-isomer) to 0.048 ng/g (Cl₁-isomer). The lower the number of chloride, the less production of PCDDs. On the other hand, there was no relation between the number of chloride and PCDF formation. The amount of PCDFs formed in the sample ranged from 8.02 ng/g (Cl₂-isomer) to 4.46 ng/g (Cl₈-isomer). A polyvinylchloride (PVC) sample produced 207 ng/g of total dioxins and a PVDC sample produced 57.4 ng/g of total dioxins when they were combusted under the same conditions. An approximately equal composition of dioxin isomers was formed from PVDC and PVC samples. Paper was found to contribute to PCDF formation when it was combusted with plastics.     

Chlorinated dibenzo-p-dioxin and dibenzofuran levels in human adipose tissue and milk samples from the north and south of Vietnam

Although 2,3,7,8-TCDD has been found to be extremely toxic to a variety of laboratory aminals, human epidemiology studies, where exposure to 2,3,7,8-TCDD has been less well characterized than in animal toxicologic studies, have been less conclusive in characterizing the extent of toxicity. In order to determine whether the newly refined techniques of human adipose tissue biopsy including isomer specific and sensitive measurement of PCDDs and PCDFs might be able to assist in finding populations within the same country with high and low levels of dioxins, adipose tissue samples were taken and levels analyzed from the north and south of Vietnam. It seemed reasonable, based on previous work, that high levels of 2,3,7,8-TCDD might still be found in adipose tissue in selected patients living in areas sprayed with Agent Orange and other 2,3,7,8-TCDD containing herbicides, and that lower levels should be found in patients not exposed to 2,3,7,8-TCDD from herbicides or other sources, such as persons who had always resided in the north of Vietnam. Of 9 specimens from patients hospitalized in Hanoi who had never been south, none had detectable adipose tissue levels of 2,3,7,8-TCDD at a detection limit of 2 or 3 ppt on a wet weight basis. Of 15 specimens from Ho Chi Minh City hospitalized patients the mean of positive specimens (12 of 15) was 28 on a lipid basis. The mean of the positive values from the south is about 2 to 3 times higher than found in the North American Continent control patients where the mean is about 6–10 ppt and much higher than in the north of Vietnam. In the northern specimens, the levels were non-detectable with a sensitivity of between 2 and 3 ppt. Other PCDD and PCDF isomers not found in Agent Orange, the penta- through octachlorinated dibenzo-dioxins and dibenzofurans, were similar in isomer type and quantity in the south of Vietnam to what we previously reported in North America. Adipose tissue from the north of Vietnam contained the lowest levels of four through eight chlorinated dioxins and furans thus far reported. The initial data suggests that populations exist in the south of Vietnam with elevated levels of 2,3,7,8-TCDD at the present time, fourteen years after the last known 2,3,7,8-TCDD (Agent Orange) application, superimposed on a preexisting body burden of dioxins and dibenzofurans from sources other than Agent Orange such as technical grade pentachlorophenol or products of incineration contaminated with higher chlorinated PCDDs or PCDFs. In light of the recent finding that unexpected levels of PCDDs and PCDFs exist in the general adult population of industrialized countries, ca. 1,000 to 1,200 ppt, wet weight of total dioxin and furan isomers in adipose tissues, it seems reasonable that the extent of human toxicity of dioxins may be more readily characterized in Vietnam than in industrialized countries. Because 2,3,7,8-TCDD was applied in 1962–1970, although not yet cleaned up, the levels of 2,3,7,8-TCDD in the environment, the food chain, and in humans, would be expected to decrease with time. Therefore, if studies are not initiated in a timely fashion, the opportunity to better characterize the extent of the toxicity of TCDD to humans as well as the persistence of TCDD in the environment in Vietnam may be lost.     

The emission inventory of PCDD/PCDF in Taiwan

Establishment of a country or region-based dioxin inventory was considered a crucial step toward elimination of worldwide dioxins/POPs contaminations, although no harmonized method for the preparation of an inventory is available at present. In this study, we used limited data and information to generate an inventory of dioxin emissions from some major sources in Taiwan. A total of 67.25 g I-TEQ of dioxins released annually was estimated. Unlike most of the industrialized countries, municipal waste incineration is not the highest contributor for dioxins released into the atmosphere. In contrast, secondary copper smelting accounts for more than 39% of the total dioxin emissions, and is higher than those from all waste incinerators combined (23.7%). Cement kilns and electric arc furnaces for steels also produced significant portion (both >10%) of dioxins into the environment, followed by secondary aluminum smelting (6.53%), industrial oil combustion (5.02%) and power plants fueled by coal (5.01%). Other known sources are either insignificant with respect to their dioxin emissions or not included in this inventory due to lack of information or uncertainty of the results. Data presented in this report provide a general picture of dioxin emissions in Taiwan, but were mostly based on less reliable or representative information, especially with respect to emission factors from different emission sources. It is necessary to establish background information relative to our own environment at present. Upon available, the inventory should be updated accordingly for proper environmental management on dioxins.     

Development of dioxin toxicity evaluation method in human milk by enzyme-linked immunosorbent assay--assay validation for human milk

In this study, the development of a toxicity evaluation method for dioxins in human milk by enzyme-linked immunosorbent assay (ELISA) was reported. A total of 17 human milk samples were tested by ELISA and by gas chromatography/mass spectrometry (GC/MS) to assess whether the ELISA performed on samples obtained from primiparas could be considered as reliable enough for identifying a dioxins contamination in human milk. The concept of toxicity equivalent quantity (TEQ) screening was validated by comparing TEQ values for a set of human milk samples to the ELISA responses predicted for those samples. A fairly good correlation (r=0.920) between immunoassay and GC/MS was achieved for human milk. This ELISA should be useful for biological samples monitoring.     

Fourth WHO-coordinated survey of human milk for persistent organic pollutants (POPs): Belgian results

Persistent organic pollutants (POPs) are chemicals that accumulate in the food chain and are toxic to humans and wildlife. The fourth World Health Organization (WHO) survey on POP levels in human milk (2006-2009) aims to provide baseline and trend information on human exposure to POPs. So far Belgium participated in all three previous rounds (1988, 1992, 2001). Whereas the first three rounds focused on determination of dioxins and PCBs in pooled (mixed) samples, the fourth survey comprised the analyses of individual milk samples for nine "basic POPs" (chlorinated pesticides and indicator PCBs) and of pooled milk samples for "basic POPs", "advanced POPs" (dioxins and dioxin-like PCBs) and "optional POPs" (polybrominated diphenylethers [PBDEs], polybrominated dioxins and dibenzofurans [PBrDD/F], mixed halogenated dioxins and dibenzofurans [PXDD/F] and hexabromocyclododecane [HBCD]). For the Belgian participation human milk samples were collected during the summer of 2006 from 197 women between 18 and 30 years old distributed over all Belgian provinces. The individual samples were analyzed in a Belgian Laboratory for "basic" POPs. A pooled sample was made from 178 individual samples and analyzed by the WHO Reference Laboratory for the "basic, advanced and optional" POPs. The results indicate that most organochlorinated pesticides banned 25-30 years ago were below or around detection limits in Belgian human milk samples although DDE was still found at low levels in all samples. Over the last five years the levels of marker PCBs and PCDD/Fs in Belgian human milk decreased, respectively, by 58% and 39%. For some of the other emerging or older compounds recent international data are needed to allow comparison. This shows the importance of international studies as run by WHO.     

碳酰肼对烧结过程二噁英生成的抑制作用

研究了碳酰肼对钢铁厂烧结工序产生的二噁英的抑制效果。结果表明,添加了0.01%(质量分数,下同)、0.02%、0.05%、0.10%的碳酰肼之后,二噁英的排放质量浓度降为0.560、0.506、0.270、0.174ng-TEQ/m3,相对于基准值(0.821ng-TEQ/m3)大幅减少。碳酰肼对二噁英的从头合成以及前驱物生成都能起到一定的抑制效果。碳酰肼与Cu2+结合生成稳定的氮化物,削弱Cu2+的催化活性;与HCl反应,减少了生成二噁英的氯源;对FeCl3、CuCl2的催化活性也会产生影响。碳酰肼添加后,对多氯代二苯并呋喃(PCDFs)生成中高氯代二噁英的脱氯行为也有明显的抑制。     

Pollutant emissions from modern incinerators

Emissions of dioxins are mainly from incinerators, domestic and industrial coal combustion, and traffic. However, the major public concern and research effort are associated with the emissions of organic micropollutants from waste incinerators. This paper gives a brief overview of the more recent research and development for the removal of dioxins and heavy metals from flue-gas streams. Special attention is devoted to the origin and control of emissions from incinerators. It appears that flue-gas cleaning systems in modern incinerators are very reliable in removing almost all polluting emissions from flue-gas streams. However, the fly ash residues generated pose a significant disposal problem, as they are enriched with heavy metals and organic micropollutants.     

An evaluation of factors affecting alumina selectivity for the isomer specific determination of 2,3,7,8-tetrachlorodibenzodioxin

Fully activated basic alumina has previously been shown to have the ability to give quantitative separation of tetrachlorodibenzo-p-dioxins (TCDDs) from polychlorinated biphenyls (PCBs) using a 12% chloroform in hexane solution. Further separation of 2,3,7,8-TCDD from other tetra isomers can be accomplished by use of 100% n-butyl chloride, 15% methylene chloride in hexane or 40% chloroform in hexane. A more complete comparison of basic alumina with acidic and neutral alumina has now been carried out. Additionally, an evaluation of this procedure for use with the other 2,3,7,8- substituted furans and dioxins has been made. Lewis base oxygen sites of the dioxin and furan molecules were used to explain the interactions observed. The alumina surface is believed to provide randomly spaced aluminum sites which act as Lewis acids in the adsorption process.