Sorption Of Hydrophobic Organic Contaminants Research Articles

Competitive sorption experiments reveal new regression models to predict PhACs sorption on carbonaceous materials

Sorption of hydrophobic organic contaminants onto thermally altered carbonaceous materials (TACM) constitutes a widely used technology for remediation of polluted waters. This process is typically described by sorption isotherms, with one of the most used models, the Polanyi-Dubinin-Manes (PDM) equation, including water solubility (Sw) as a normalizing factor. In case of pharmaceutical active compounds (PhACs), Sw depends on the pH of the environment due to the ionic/ionizable behavior of these chemicals, a fact frequently ignored in sorption studies of PhACs. In this work, we set the theoretical framework to include the variation of Sw with pH in the definition of the PDM model, and we applied this approach to describe the effect of ambient pH in the competitive sorption of three commonly detected PhACs (carbamazepine, ibuprofen, and sulfamethoxazole) onto three carbonaceous sorbents (biochar, powder activated carbon, and colloidal activated carbon). Changes in the ambient pH and hence in the hydrophobicity of the compounds could explain the strong variations observed in single-solute sorption and also in competitive sorption. Furthermore, Sw was used as a parameter for the linear regression model of sorption coefficients of our experiments, suggesting the incorporation of this variable as an improvement to existing approaches for prediction of PhACs sorption onto TACM.

A machine learning and experimental-based model for prediction of soil sorption capacity toward phenanthrene

Sorption by soil is the fundamental basis for environment fate of hydrophobic organic contaminants (HOCs), which varies significantly depending on diverse properties of soils. Therefore, a generalized approach to predict HOC sorption by soils is required. In this study, 488 data points were extracted from references and adopted to develop models for estimating the sorption capacities of phenanthrene in soils using six different machine learning (ML) approaches. The extreme gradient boosting (XGBT) model demonstrated the most favorable performance, achieving a coefficient of determination of 0.91 and root-mean-square errors of 0.24 for the testing dataset. The XGBT model's performance was further demonstrated by comparing with experimental data from batch sorption tests conducted on 20 soil samples collected from 17 provinces of China. The differences between the predicted values and the experimental values were statistically equal to zero (p = 0.14). Leveraging the XBGT model together with soil properties from the Harmonized World Soil Database, the distribution of sorption capacities in Chinese soils was successfully depicted on a national scale. This research is expected to contribute to a deeper understanding of the migration of persistent organic pollutants in terrestrial system. Furthermore, the established model holds implications for more precise and scientific soil environmental management.

Total organic carbon content as an index to estimate the sorption capacity of micro- and nano-plastics for hydrophobic organic contaminants

The worldwide existing micro- and nano-plastics (MNPs) showed high sorption capacity for hydrophobic organic contaminants (HOCs), and thus leading to change of the environmental behaviors and fates of HOCs. However, there is a lack of general index for evaluating the sorption capacity of MNPs for HOCs. Herein, we investigated the sorption of chlorobenzene, naphthalene and phenanthrene to 10 MNPs of different polymer types with and without UV-aging, respectively. It was found that the sorption was well fitted by Freundlich isotherm model with coefficients R2 in the range of 0.892–1.00, and aging of most MNPs resulted in decreased sorption capacity for naphthalene and phenanthrene but slightly increased sorption capacity for chlorobenzene. More importantly, for the 8 MNPs commonly present in the environment and with measured total organic carbon (TOC) covering the range of 23.0–91.9%, the logarithm sorption constant (logKd) values of the studied HOCs positively correlated with TOC contents of MNPs, with a good determination coefficient (R2) of 0.923 for naphthalene, 0.694 for chlorobenzene, and 0.565 for phenanthrene. Our study demonstrated that the TOC content of MNPs is a good index for estimating the contribution of total MNPs to the sorption of nonpolar HOCs in the environmental media.

Microplastic properties and their interaction with hydrophobic organic contaminants: a review

Microplastics (MPs) have been defined as particles of size < 5mm and are characterized by hydrophobicity and large surface areas. MPs interact with co-occurring hydrophobic organic contaminants (HOCs) via sorption-desorption processes in aquatic and terrestrial environments. Ingestion of MPs by living organisms may increase exposure to HOC levels. The key mechanisms for the sorption of HOCs onto MPs are hydrophobic interaction, electrostatic interaction, π-π interactions, hydrogen bonding, and Van der Waals forces (vdW). Polymer type, UV-light-induced surface modifications, and the formation of oxygen-containing functional groups have a greater influence on electrostatic and hydrogen bonding interactions. In contrast, the formation of oxygen-containing functional groups negatively influences hydrophobic interaction. MP characteristics such as crystallinity, weathering, and surface morphology affect sorption capacity. Matrix properties such as pH, ionic strength, and dissolved organic matter (DOM) also influence sorption capacity by exerting synergistic/antagonistic effects. We reviewed the mechanisms of HOC sorption onto MPs and the polymer and matrix properties that influence the HOC sorption. Knowledge gaps and future research directions are outlined.

Sorption mechanism of naphthalene by diesel soot: Insight from displacement with phenanthrene/p-nitrophenol

The nonlinear sorption of hydrophobic organic contaminants (HOCs) could be changed to linear sorption by the suppression of coexisting solutes in natural system, resulting in the enhancement of mobility, bioavailability and risks of HOCs in the environment. In previous study, inspired from the competitive adsorption on activated carbon (AC), the displaceable fraction of HOCs sorption to soot by competitor was attributed to the adsorption on elemental carbon fraction of soot (EC-Soot), while the linear and nondisplaceable fraction was attributed to the partition in authigenic organic matter of soot (OM-Soot). In this study, however, we observed that the linear and nondisplaceable fraction of HOC (naphthalene) to a diesel soot (D-Soot) by competitor (phenanthrene or p-nitrophenol) should be attributed to not only the linear partition in OM-Soot, but also the residual linear adsorption on EC-Soot. We also observed that the competition on the surface of soot dominated by external surface was different from that of AC dominated by micropore surface, i.e., complete displacement of HOCs by p-nitrophenol could occur for the micropore surface of AC, but not for the external surface of soot. These observations were obtained through the separation of EC-Soot and OM-Soot from D-Soot with organic-solvent extraction and the sorption comparisons of D-Soot with an AC (ACF300) and a multiwalled carbon nanotube (MWCNT30). The obtained results would give new insights to the sorption mechanisms of HOCs by soot and help to assess their environmental risks.

Sorption fractionation of bacterial extracellular polymeric substances (EPS) on mineral surfaces and associated effects on phenanthrene sorption to EPS-mineral complexes

Microbial extracellular polymeric substances (EPS) represent an important source of labile component in natural organic matter (NOM) pool. However, the sorption behavior of EPS to mineral surfaces and associated effects on sorption of hydrophobic organic contaminants (HOCs) are not well understood. Here, we systematically investigated the fractionation of EPS extracted from two different microbial sources (Gram-positive B. subtilis and Gram-negative E. coli) during sorption to montmorillonite, kaolinite, and goethite using collective characterization methods (SEM, electrophoretic mobility, FTIR, 1H NMR, UV–vis, fluorescence, and size exclusion chromatography). The peptide-like substances and acidic components with high aromaticity in B. subtilis EPS were more preferentially sorbed than those fractions in E. coli EPS by the three minerals, especially by goethite. Additionally, goethite sorbed more negatively charged and lower molecular weight fractions compared to montmorillonite. The presorption of EPS (1.68–3.79% organic carbon) on the three minerals increased the sorption distribution coefficient (Kd) of phenanthrene (a model apolar HOC) by 2.83–5.29 times, depending on the EPS-mineral complex. All the six examined EPS-mineral complexes exhibited approximately one order of magnitude larger organic carbon (OC)-normalized sorption coefficient (KOC) than the two pristine EPS, indicating that the sorptive interactions were pronouncedly facilitated by the sorbed EPS on mineral surfaces. Thus, the type and surface property of minerals as well as the biological source of EPS are key determinants of sorption fractionation of EPS on minerals and in turn affect sorption affinity of apolar HOCs to EPS-mineral complexes.

A rapid experimental protocol to determine the desorption resistant fraction of sediment-sorbed hydrophobic organic contaminants.

Desorption of hydrophobic organic contaminants (HOCs) from sedimentary materials plays a vital role in dictating the fate and transport of HOCs in the environment. Desorption irreversibility is a commonly observed phenomenon in laboratory sorption/desorption studies of HOCs. A desorption-resistant fraction (DRF) typically exists during the desorption process. To correctly evaluate the DRF of HOCs can considerably contribute to the understanding of availability and bioavailability of HOCs. This can substantially benefit contaminant remediation and cleanup operations. Conventional batch method to measure the DRF replies on repetitive washing of the sediments, which is time-consuming and can be impractical. This study presents an experimental protocol to quantify the DRF of the sediment-sorbed organic contaminants in a rapid manner. This protocol utilizes cosolvent to expedite desorption kinetics and adopts an ultrafiltration/centrifugation combined method to achieve a complete separation of sediment and solution phases. This proposed experimental protocol can facilitate the quantification of the DRF of sorbed contaminants to understand and minimize the uncertainties associated with risk-based pollution remediation approach. This protocol has the potential to be widely used in environmental studies to characterize sorption and desorption properties of HOCs with soil and sedimentary materials.

Sorption of pentachlorophenol and phenanthrene by humic acid-coated hematite nanoparticles

Hematite nanoparticles (NPs) exist naturally and ubiquitously in soil, and they are always associated with soil organic matter by forming organic-inorganic complexes. In this work, hematite NPs coated with peat humic acid (HApeat) and soil humic acid (HAsoil) were chosen as sorbents for hydrophobic organic contaminants (HOCs) to simulate the sorption processes in soil. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative HOCs. Compared with sorption isotherms of uncoated hematite NPs, the coating of HA onto the surface of hematite NPs substantially increased its sorption affinity for PCP and PHE by about 1-2 orders of magnitude, and the increasing degree was positively correlated to the HA content. These phenomena emphasized the dominant role of HA in the sorption process. The reduced polarity and the introduction of functional groups contributed to the enhanced sorption of HOCs on HA-coated hematite NPs. Furthermore, HApeat-hematite NPs showed higher sorption affinity for both PCP and PHE than HAsoil-hematite NPs, which was mainly due to the lower polarity and higher hydrophobicity of HApeat-hematite NPs. The sorption of PCP and PHE on HA-coated hematite NPs was inhibited obviously with increasing pH values and the pH effect on PCP sorption was more significant than that of PHE, due to the deprotonation of functional groups within adsorbed HA, the loose structure of adsorbed HA and the dissociation of PCP. Our findings elucidated the mechanisms involved in HOCs sorption processes by HA-hematite NPs and provided a theoretical basis for environmental remediation with natural NPs (e.g., hematite NPs).

Sorption of hydrophobic organic contaminants on functionalized biochar: Protagonist role of π-π electron-donor-acceptor interactions and hydrogen bonds.

The sorption of five potent endocrine disruptors as representative hydrophobic organic contaminants (HOCs) namely estrone (E1), 17β-estradiol (E2), estriol (E3), 17α-ethynylestradiol (EE2) and bisphenol A (BPA) on functionalized biochar (fBC) was systematically examined, with a particular focus on the importance of π-electron-donor (phenanthrene: PHEN) and π-electron-acceptors (1,3-dinitrobenzene: DNB, p-amino benzoic acid: PABA) on sorption. Experimental results suggested that hydrogen-bond formation and π-π-electron-donor-acceptor (EDA) interactions were the dominant sorption mechanisms. The sorption of HOCs decreased as E1 > E2 > EE2 > E3 > BPA based on the Freundlich and Polanyi-Mane-models. The comparison of adsorption coefficient (Kd) normalized against hexadecane-water partition coefficient (KHW) between HOCs and PHEN indicated strong π-π-EDA interactions. π-π interactions among DNB, PHEN and HOCs were verified by the observed upfield frequency (Hz) shifts using proton nuclear magnetic resonance (1H NMR) which identified the specific direction of π-π interactions. UV-vis spectra showed charge-transfer bands for π-donors (PHEN and HOCs) with the model π-acceptor (DNB) also demonstrating the role of π-π EDA interactions. The role of π-electron-donor and π-electron-acceptor domains in fBC was identified at different solution pH.

Role of biochar in biodegradation of nonylphenol in sediment: Increasing microbial activity versus decreasing bioavailability

The observed strong sorption of hydrophobic organic contaminants (HOCs) to biochar presents potential implications for HOCs bioavailability and bioaccessibility in sediments, while biochar could impact sediment microbial ecology. However, the comprehensive study on the effects of biochar on HOC biodegradation coupled with bioavailability and microbial ecology are rarely documented. In this paper, the effects of biochar on the biodegradation of nonylphenol (NP) were investigated using 3 different NP concentrations (20, 50 and 500 mg/Kg) in sediments amended with different percentage of rice straw biochar (RC). Results showed that the influence of RC on NP biodegradation varied with different NP concentrations. At low NP concentrations, RC suppressed NP biodegradation by reducing NP bioavailability, while at high NP concentrations, moderate RC addition promoted biodegradation by reducing toxicity of NP to microbes. The effects of NP on microbial community structures were significant (P < 0.01), but those of RC were not significant (P > 0.05). The RC affected microorganisms through altering NP toxicity, microbial quantity and activity, but not microbial community structures. This study indicated that there could be an optimal biochar percentage in biochar-sediment systems at different HOC concentrations, which strengthened HOC biodegradation process and accelerated biodegradation rate, forming adsorption-biodegradation coupled bioremediation.

Characterization and phthalate esters sorption of organic matter fractions isolated from soils and sediments

The sorption of two phthalate esters (PAEs) and phenanthrene (PHE) by different natural organic matter fractions (NOMs) was examined. The surface area of the NOMs correlated positively with the starting decomposition temperature (SDT), implying increased number of micropores with the rise of condensation. Sorption of PHE on nonhydrolyzable carbons (NHCs) and other NOMs was respectively dependent on aromatic and aliphatic C contents. Likely physical blocking of the aliphatic moieties and input of black carbon materials led to elevated sorption capacity for PHE of aromatic domains in the NHCs. Sorption of PAEs by NOMs excluding NHCs was jointly regulated by hydrophobic partitioning and H-bonding interactions. The SDT of the NOMs correlated negatively with the Koc when SDT ≥304 °C, likely because the highly condensed domains may impair the availability of amorphous moieties for sorption. This study highlights the influence of domain accessibility of NOMs on sorption of hydrophobic organic contaminants.

Efficient chemical oxidation of high levels of soil-sorbed phenanthrene by ultrasound induced, thermally activated persulfate

The sorption of hydrophobic organic contaminants (HOCs) and limited mass transfer in heterogeneous subsurface environment are major hurdles to efficient remediation of highly contaminated sites by traditional activated persulfate. In this work, ultrasound was coupled to persulfate oxidation to enhance the remediation. The mechanisms of the coupling process were investigated, using soil spiked with high levels of phenanthrene as a model compound for PAHs and other HOCs. The results indicate that, when ultrasound is applied to the soil slurry, the resultant heat, due to the ultrasonic energy absorbed by the soil particles, activates persulfate to generate sulfate radicals to oxidize the dissolved phenanthrene, and the dissolution and desorption of the phenanthrene are also enhanced by elevated temperature, ultrasound itself and the oxidation by persulfate, thereby creating a positive-feedback loop that induces rapid and highly efficient oxidation of the contaminants. Furthermore, the effects of ultrasound intensity, contaminant concentration, oxidant dosage, soil to water ratio, and addition of external activators on the oxidation of phenanthrene were also studied. For potential field applications, coupling downhole ultrasound technologies with traditional persulfate process was proposed to facilitate the remediation of HOCs contaminated sites.

Cr and As decrease lindane sorption on river solids

The fate of a pollutant in water is modified by sorption onto solids and by interaction with other pollutants. Actual knowledge is mainly focussed on pollutant sorption by sediments, whereas little is known about the roles of natural biofilms and suspended particles. Moreover, few investigations report on the interaction of co-occurring pollutants. Here, we studied the sorption of the lindane pesticide by natural biofilms, suspended particles, and river sediments using batch experiments. We also measured the effects of Cr(VI) and As(V) on lindane sorption. Results show that more lindane is adsorbed by biofilms than by suspended particles and sediments on a total mass basis, whereas the sediments had a higher lindane sorption capacity per unit mass organic carbon than suspended particles and biofilms. Co-occuring Cr(VI) or As(V) decreased lindane sorption on the biofilms by about 48 %. To our best knowledge, this is the first report showing that Cr(VI) and As(V) decrease the sorption of hydrophobic organic contaminants on river solids.

Effect of model dissolved organic matter coating on sorption of phenanthrene by TiO2 nanoparticles

Dissolved organic matter (DOM) may alter the sorption of hydrophobic organic contaminants (HOC) to metal oxide nanoparticles (NPs), but the role of DOM and NP types is poorly understood. Here, phenanthrene sorption was quantified on four types of nano-TiO2 (three rutile, one anatase), and a bulk, raw TiO2 powder. Prior to the sorption experiments, these nanoparticles were coated using four different organic materials: Lignin (LIG), tannic acid (TAN), Congo red (CON), and capsorubin (CAP). Lignin, tannic acid, congo red and capsorubin coating substantially enhanced phenanthrene sorption to various TiO2 particles. After coating with a specific DOM, Kd values by the DOM-coated TiO2 particles on percent organic carbon content and surface area (SA) basis (Koc/SA) generally followed the order: TiO2 NPs with hydrophobic surfaces > bulk TiO2 particles > other TiO2 NPs. Different Koc/SA values of various DOM-TiO2 complexes resulted from distinct conformation of the coated DOM and aggregation.

Effect of cosolutes on the sorption of phenanthrene onto mineral surface of river sediments and kaolinite.

Sorption of phenanthrene onto the natural sediment with low organic carbon content (OC%), organic-free sediment, and kaolinite was investigated through isotherm experiments. Effects of cosolutes (pyrene, 4-n-nonyphenol (NP), and humic acid (HA)) on phenanthrene sorption were also studied by comparing apparent solid-water distribution coefficients (K d app) of phenanthrene. Two addition sequences, including “cosolute added prior to phenanthrene” and “cosolute and phenanthrene added simultaneously,” were adopted. The Freundlich model fits phenanthrene sorption on all 3 sorbents well. The sorption coefficients on these sorbents were similar, suggesting that mineral surface plays an important role in the sorption of hydrophobic organic contaminants on low OC% sediments. Cosolutes could affect phenanthrene sorption on the sorbents, which depended on their properties, concentrations, and addition sequences. Pyrene inhibited phenanthrene sorption. Sorbed NP inhibited phenanthrene sorption at low levels and promoted sorption at high levels. Similar to NP, effect of HA on phenanthrene sorption onto the natural sediment depended on its concentrations, whereas, for the organic-free sediment and kaolinite, preloading of HA at high levels led to an enhancement in phenanthrene K d app while no obvious effect was observed at low HA levels; dissolved HA could inhibit phenanthrene sorption on the two sorbents.

The Influence of Black Carbon on the Sorption and Desorption of Two Model PAHs in Natural Soils

Black carbons (BC) which result from the incomplete combustion of farm waste [man-made (burned) BC] are highly absorbent. In Taiwan, the burning of farm waste known as slash and burn is common. The BCs from the burning may present an environmental challenge. Little is known about the effect of BCs on the transport of hydrophobic organic contaminants (HOC). This study investigates the sorption of anthracene and naphthalene to BCs in soil and efficiency of the surfactants Tween 80 and Triton X-100 in their removal. Both surfactants demonstrated 2-6 times increased solubility in the soils with the addiction of BC. Column experiments were performed to imitate the transportation of these contaminants in groundwater through soils before and after adding BC produced by burning farm waste in the lab. We found significantly increased sorption of anthracene in soil added with BCs produced in the lab, suggesting that fraction of organic carbon (foc) can contribute to sorption of such HOCs. Sorption of naphthalene was increased but not significantly. Comparing the concentrations of contaminants, we found the soil containing BC from burned farm waste absorbed HOC more efficiently than the organic BC (naturally-occurring) in the original soil. Therefore, sorption capacity and influence on the transport of HOC cannot be estimated simply by the foc of the soil because the two BCs differ greatly in their sorption ability. BC from farm waste absorbs more contaminants than naturally occurring BC in the soil.

Effects of varying estuarine conditions on the sorption of phenanthrene to sediment particles of Yangtze Estuary

The sorption of phenanthrene on the Yangtze Estuary sediment was studied under varying conditions of particle size, sediment organic contents, salinity, and dissolved organic matter (DOM) concentrations. Small sediment particles showed higher trapping capacity for phenanthrene due to the higher organic contents associated. The organic carbon-based partition coefficient of phenanthrene to the Yangtze Estuary sediment was obtained as 7120L/kg, lower than the values for other soils or sediments reported in previous studies. The magnitude and direction of the salt effect were complicated by the specific DOM studied. The sediment sorption capacity was greatly increased in saline water in the absence of DOM but decreased in the presence of DOM. Given the conditions in the Yangtze Estuary, the equilibrium sorption of phenanthrene would be decreased with increasing salinity. Overall, the nature and content of both sediment-bound and dissolved organic matter dominate the sorption of hydrophobic organic contaminants in the estuary.

Impact of Deashing Treatment on Biochar Structural Properties and Potential Sorption Mechanisms of Phenanthrene

Knowledge of the mineral effects of biochars on their sorption of hydrophobic organic contaminants (HOCs) is limited. Sorption of phenanthrene (PHE) by plant-residue derived biochars (PLABs) and animal waste-derived biochars (ANIBs) obtained at two heating treatment temperatures (HTTs) (450 and 600 °C) and their corresponding deashed biochars was investigated. The decreased surface polarity and increased bulk polarity of biochars after deashing treatment indicated that abundant minerals of biochars benefit external exposure of polar groups associated organic matter (OM). Organic carbon (OC)-normalized distribution coefficients (K(oc)) of PHE by biochars generally increased after deashing, likely due to enhancement of favorable and hydrophobic sorption sites caused by mineral removal. Positive correlation between PHE log K(oc) by PLABs and bulk polarity combined with negative correlation between PHE log K(oc) values by ANIBs and surface polarity suggested PLABs and ANIBs have different sorption mechanisms, probably attributed to their large variation of ash content because minerals influenced OM spatial arrangement within biochars. Results of this work could help us better understand the impact of minerals, bulk/surface polarity, and sorption domain arrangement of biochars on their HOCs sorption and predict the fate of HOCs in soils after biochar application.

Impact of organic matter properties on sorption domains of phenanthrene on chemically modified geosorbents and synthesized charcoals

To study the impact of organic matter (OM) properties on different sorption domain of hydrophobic organic contaminants, phenanthrene sorption on chemically modified geosorbents and synthesized charcoals (SCs) was investigated and explored using Dual-Mode model (DMM). Sorption of phenanthrene on two geosorbents, peat and lignite, and their modified forms by hydrolysis, oxidation, and oximation, as well as on three SCs with different pyrolytic degrees changed were significantly affected by the aromaticity (A) and polarity index (PI) of OM. Positive correlation between OM normalized parameter of Langmuir sorption capacity of DMM (SDM/fOM) and A×PI−1 was observed. To distinguish the deviation of DMM, SDM was corrected by assigning the Langmuir affinity parameter (bDM) of DMM to the high energy Langmuir affinity parameter (bH) in Dual-Langmuir model (DLM). More significant correlation was observed between A×PI−1 and corrected SDM, which confirms that the nonpolarity and aromaticity of sorbent OM contribute much to the hydrophobic organic contaminants sorption with high energy. Besides, the partition coefficient of linear domain of DMM normalized by OM (KP/fOM) was positively related to PI−1 rather than negatively related to PI, suggesting that PI−1 is more suitable than −PI to evaluate the nonpolarity of sorbent OM.

Responses of Lumbriculus variegatus to Activated Carbon Amendments in Uncontaminated Sediments

Activated carbon (AC) amendment is a recently developed sediment remediation method. The strong hydrophobic organic contaminant sorption efficiency of AC has been shown in several studies, but effects on benthic organisms require more investigation. The AC induced effects on egestion rate, growth and reproduction of Lumbriculus variegatus were studied by applying bituminous coal based AC in three different particle size fractions, namely <63 μm (90%, AC(p)), 63-200 μm (AC(m)) and 1000 μm (AC(g)), to natural uncontaminated (HS) and artificial sediment (AS). Egestion rate, growth and reproduction decreased with increasing AC concentration and finer AC particle fractions, effects being stronger on HS than on AS sediment. Lipid content in AS was reduced already at the lowest AC doses applied (AC(p) and AC(m) 0.05%, AC(g) 0.25%). In addition, hormesis-like response was observed in growth (AS) and reproduction (AS, HS) indicating that AC may disturb organisms even at very low doses. Potential ecological effects need to be further evaluated in an amendment- and site-specific manner.