Influence Of Ionic Strength Anions And Cations Biology Essay
The surface assimilation of four wide-use pharmaceuticals ( carbamazepine, diclofenac, isobutylphenyl propionic acid, and Orudis ) onto a porous silicon oxide was investigated under varied ionic strengths, different anions, bivalent cations ( Ca2+ and Mg2+ ) , trivalent cations ( Al3+ and Fe3+ ) , and natural organic affair ( NOM ) . The experiments demonstrated that at a given pH the surface assimilation was most affected by ionic strength, trivalent cations, and belongingss of pharmaceuticals.
The addition of ionic strength resulted in an addition in the surface assimilation of Orudis, but a lessening in the surface assimilation of carbamazepine. Trivalent metal cations made intense additions in the surface assimilation of three acidic pharmaceuticals, which could be due to the formation of inner-sphere composite of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the surface assimilation of carbamazepine was non affected by divalent and trivalent cations, whereas the surface assimilation of diclofenac was entirely impacted by the presence of Al3+ . Furthermore, bivalent cations at low concentration could somewhat heighten the surface assimilation of isobutylphenyl propionic acid and Orudis, whereas NOM caused a decrease in the surface assimilation of the tried pharmaceuticals except for diclofenac. These consequences suggest that ionic strength, divalent cations, trivalent cations, and NOM are noteworthy factors impacting the surface assimilation of pharmaceuticals and therefore the ultimate destiny of pharmaceuticals in the aqueous environment.
The omnipresent presence of pharmaceuticals in the environment ( Halling-Sorensen et al. , 1998 ; Fent et al. , 2006 ) has raised a figure of critical concerns, including their destiny in dirt and H2O ( Halling-Sorensen et al. , 1998 ; Heberer, 2002 ; Loffler et al. , 2005 ) . The environmental destiny of pharmaceuticals can be strongly influenced by their surface assimilation to dirt and deposit ; surface assimilation influences the distribution of substances between aqueous stage and solid surfaces, which in bend affects their conveyance in an aqueous environment and regulates their ultimate destiny. Adsorption behaviour of pharmaceuticals in H2O is controlled by adsorbent belongingss, pharmaceutical belongingss ( e.g.
, H2O solubility, hydrophobicity, and acid/base belongingss ) , and H2O features ( e.g. , pH, ionic strength, cations, anions, and natural organic affair ( NOM ) ) .
To day of the month, several studies related to the surface assimilation of pharmaceuticals to natural stuffs or constituents of natural stuffs have been published. Soils ( Figueroa and MacKay, 2005 ) , clays ( Figueroa et al. , 2004 ; Pils and Laird, 2007 ) , and hydrated oxides ( Gu and Karthikeyan, 2005a ) have been investigated for the surface assimilation of Achromycin. In add-on, since silicon oxide is a major constituent of the harsh clay fraction of many dirts, the surface assimilation of several pharmaceuticals onto silicon oxide has been explored ( Goyne et al. , 2005 ; Turku et al. , 2007 ; Bui and Choi, 2009 ) .The probe of the consequence H2O features on the surface assimilation of pharmaceuticals is indispensable in order to gauge their ultimate destiny. To this terminal, except for pH, common in most studies, old surveies in this country have reported on the effects of ionic strength, Ca cations, and humic substances on pharmaceutical surface assimilation.
An addition of ionic strength consequences in less overall sorption of Terramycin on clays ( Figueroa et al. , 2004 ) and the reduced sorption of Achromycin on silicon oxide ( Turku et al. , 2007 ) . At low United States Public Health Service, clay treated with Ca2+ showed lower sorption with Terramycin than clays treated with Na+ ( Figueroa et al. , 2004 ) , though a contrary consequence was observed at a pH above 7.
Humic acid at a concentration of 1 mg/L increased the sorption of Terramycin on clay, whereas 10 mg/L of humic acid decreased it ( Kulshrestha et al. , 2004 ) . In add-on, the surface assimilation of humic substances on clay suppressed tetracycline sorption ( Pils and Laird, 2007 ) . However, the influence of all factors including pH, ionic strength, anions, cations, and NOM on the surface assimilation of pharmaceuticals has been seldom evaluated.Carbamazepine ( an anticonvulsant ) , diclofenac, ibuprofen, and Orudis ( nonsteroidal anti-inflammatory drugs ) are four pharmaceuticals that are widely used and ubiquitously detected in aqueous environments ( Halling-Sorensen et al. , 1998 ; Fent et al.
, 2006 ) . These pharmaceuticals are besides considered compounds that have a high environmental hazard ( Risk Quotient & gt ; 1 ) ( Hernando et al. , 2006 ) . Therefore, this survey was initiated to find the influence of H2O features on the surface assimilation of these pharmaceuticals to silica. In our research, we aim to look into the impact of different ionic strengths ( 0-50 millimeter ) , anions ( nitrate, hydrogen carbonate, sulphate, phosphate, and silicate ) , alkaline-earth cations ( Ca2+ , Mg2+ ) , trivalent cations ( Al3+ , Fe3+ ) , and NOM ( Suwannee River fulvic acid ( FA ) , Suwannee River humic acid ( HA ) , Suwannee River NOM ) on the surface assimilation of pharmaceuticals on silicon oxide.
2. Materials and Methods
Chemicals and adsorbent
All chemicals used in this survey are reagent class and purchased from Sigma-Aldrich, Junsei, Oriental Chemical Industries, and BASF. Suwannee River NOM ( catalog no. 1R101N ) , Suwannee River FA ( catalog no. 2S101F ) , and Suwannee River HA ( catalog no. 2S101H ) were purchased from the International Society of Humic Substances ( ISHS ) and used as received ; the analytical information of these NOM can be found in the Auxiliary Information ( SI ) . In add-on, high pureness ( & gt ; 99 % ) carbamazepine, diclofenac, isobutylphenyl propionic acid, and Orudiss were purchased from Aldrich. The molecular construction and physicochemical belongingss of the pharmaceuticals are summarized in Table 1. Note that stock solutions of the pharmaceuticals were made in de-ionized H2O, with the add-on of a little fraction of HPLC class methyl alcohol ( Fisher Scientific ) .
Mesoporous silicon oxide was prepared utilizing a non-ionic templet ( Zhao et al. , 1998 ) . The synthesized stuff was so characterized by X-ray diffraction, transmittal negatron microscopy, N2 adsorption-desorption measurings, and point of zero charge ( PZC ) measurings ; a more elaborate word picture of the silicon oxide is described elsewhere ( Bui and Choi, 2009 ) . The Brunauer-Emmett-Teller ( BET ) specific surface country, pore volume, and pore size of the silicon oxide was estimated as 737 m2/g, 1.
03 cm3/g, and i??8 nm, severally, and the PZC of the silicon oxide was determined to be 4.0 A± 0.1.
2.2. Batch surface assimilation experiments
Batch surface assimilation of the pharmaceuticals was conducted in 40-mL gold phials, in which working solutions were prepared with a known sum of inorganic salts and/or NOM in a buffer solution ( 2 mM 2-morpholinoethanesulfonic acid ( MES ) at pH 5.
3 ) . The solution pH could so be adjusted by adding HCl or NaOH 0.1 M as needed. Previously, MES was reported to hold a minimum consequence on the sorption of organic compounds to minerals ( Nowack et al. , 1996 ) and really weak complexing belongingss ( Good et al.
, 1966 ) . Following, stock solutions of pharmaceuticals were spiked to do an initial concentration of 100 Aµg L-1 ; to this solution 10 milligram of silicon oxide was added to achieve a solid: liquid ratio of 1 g/L. Note that clean solutions ( pharmaceuticals without silicon oxide ) were prepared in analogue with every sample. The samples and spaces were later agitated in an brooder at 200 revolutions per minute for 24 H at 25 oC. Aliquots were taken at the terminal of the 24 H period, filtered through a 0.45-Aµm cellulose ethanoate membrane filter ( MFS ) , and analyzed by LC-tandem MS. All experiments were performed in extra or triplicate.
Different working solutions were utilized to look into the influence of chemicals in the solutions on the surface assimilation of pharmaceuticals on silicon oxide. Here, the consequence of ionic strength on the pharmaceutical surface assimilation was determined utilizing inert electrolyte KCl solutions ( 0-50 millimeter ) . The impact of different anions on the surface assimilation of pharmaceuticals was so investigated by utilizing solutions incorporating 1 mM Na salts of nitrate, hydrogen carbonate, sulphate, phosphate, or silicate anions. In add-on, chloride solutions of cations such as Ca, Mg, aluminium, and ferrous ions were prepared to gauge their effects on surface assimilation. Cation concentrations were selected such that they were consistent with those in natural H2O ( Hem, 1985 ) ; 1-5 millimeter solutions were applied for bivalent cations ( Ca2+ and Mg2+ ) and a 0.
1 millimeter solution was used for trivalent cations ( Al3+ and Fe3+ ) . To see the NOM impact, solutions of 5 and 10 mg L-1 of Suwannee River NOM, Suwannee River FA, and Suwannee River HA at a entire ionic strength of 10 millimeter ( KCl ) were prepared.
2.3. Sample readying and analysis
Prior to analysis, the obtained filtrate was acidified utilizing formic acid, spiked with matching alternate criterions ( 10,11-dihydrocarbamazepine ( DHC ) for carbamazepine, 2- ( 3-chlorophenoxy ) propionic acid ( cloprop ) for the other pharmaceuticals ) and extracted via solid stage extraction techniques ( 60 milligram Waters Oasis HLB cartridges ) to guarantee that samples would be free of other organic compounds that could interfere the analysis or inorganic ions that could disintegrate the column.
Following, pharmaceuticals were analyzed on an LC-tandem MS system equipped with an HPLC Waters 2695 Separations Module accompanied with a Waters 2996 PAD, a mass spectrometer ( Waters ( Micromass ) Quattro micro API ) , and an X-Terra MS C18 column ( Waters, 50 ten 2.1 millimeter I.D. , 5 Aµm, 125 A , endcapped C18 intercrossed atoms ) . The mass spectrometer was run in ESI positive manner for carbamazepine, Orudis, and DHC and in ESI negative for diclofenac, isobutylphenyl propionic acid, and cloprop.
Multiple reaction monitoring ( MRM ) was used to place the compounds. Dwell times varied from 0.3 to 0.
5 s depending on analytes. The experimental inside informations of sample readying and analytical methods are described elsewhere ( Bui and Choi, 2009 ) . Note that each sample was analyzed two times and the obtained values were averaged.
2.4. Data computation and analysis
The per centum of surface assimilation of each pharmaceutical was calculated based on the difference between the concentration in the sample and the corresponding space. Data sets were so analyzed and plotted utilizing Sigma Plot version 11.
0 ( SPSS Inc. , CA, USA ) and Excel 2007 ( Microsoft Corporation, WA, USA ) package bundles ; differences between the samples at different ionic strengths were later evaluated utilizing a one-way analysis of discrepancy ( ANOVA ) in concurrence with all pairwise multiple comparing processs ( Tukey Test ) . In add-on, a one-way ANOVA based on multiple comparings versus the control group ( Dunnett ‘s Method ) was so used to gauge the difference between the samples and a control sample, which was applied to analyze the effects of anions, cations, and NOM. The samples in which the working solution contained merely KCl and the buffer were used as ‘controls ‘ , supplying that the ionic strength of a sample and its control were close to each other. As such, the control for the samples incorporating 1 millimeter of anions was the sample of 1 millimeter of KCl ; likewise, the control for samples incorporating 0.1 millimeter of trivalent cations, 1 millimeter of bivalent cations, and 5 millimeter of bivalent cations were the samples holding 0, 1, and 10 millimeter KCl, severally. The control for the sample incorporating NOM was the sample with 10 millimeters KCl.
Consequences and treatment
3.1. Consequence of ionic strength
Fig. 1 shows the per centum of surface assimilation of four pharmaceuticals onto the porous silicon oxide at different ionic strengths ( 0-50 millimeter ) . The surface assimilation of diclofenac is seen to expose a similar tendency as the surface assimilation of Orudis, whereas the surface assimilation behaviours of carbamazepine and ibuprofen show similarity. The ANOVA trial consequences indicate that ionic strength did non ensue any statistically important alteration ( P & gt ; 0.05 ) in the surface assimilation of diclofenac and isobutylphenyl propionic acid. However, the addition of ionic strength from 0-1 to 20-50 millimeter caused a important impact ( p & lt ; 0.
05 ) on the surface assimilation of carbamazepine and Orudis. The ANOVA consequences besides demonstrated that fluctuation of the ionic strength in smaller scopes did non bring forth a important consequence ( P & gt ; 0.05 ) on the surface assimilation, thereby back uping the postulate that little differences in ionic strength between the samples and controls presented in the following subdivisions can be neglected.Based on their pKa values ( Table 1 ) , carbamazepine is a impersonal compound, though a big fraction of diclofenac, isobutylphenyl propionic acid, and Orudiss are deprotonated and negatively charged in the media ( pH 5.
3 ) . As the ionic strength was increased from 0 to 20-50 millimeter, the surface assimilation of impersonal carbamazepine somewhat decreased ( p & lt ; 0.05 ) , whereas the surface assimilation of negatively charged Orudis increased slightly ( p & lt ; 0.05 ) .
Gao and Pedersen ( 2005 ) besides demonstrated that the addition of ionic strength lowered the surface assimilation of uncharged sulfamezathine to montmorillonite but increased the surface assimilation of anionic sulfamezathine.Adsorption behaviour of silicon oxide in an aqueous solution is mostly dependent on its ionisation and surface charge ( Papirer, 2000 ) . Since the silicon oxide in this survey has a PZC of 4.0, its surface is negatively charged in the media ( pH 5.
3 ) ; nevertheless, the surface charge of silicon oxide is low over a big pH scope ( 2-6 ) due to its hapless ionisation ( Persello, 2000 ) . In add-on, when the ionic strength additions, three procedures may happen ( Gao et al. , 2008 ) : 1 ) more surface silanols are ionized through the undermentioned equilibrium: i‚?SiOH + K+i‚?SiO-aˆ¦K+ + H+ ; 2 ) the solubility of pharmaceuticals could be influenced in such a manner that a higher ionic strength may take down the solubility of impersonal pharmaceuticals but bring on the disintegration of ionizable acidic pharmaceuticals ( Chan and Heng, 2005 ) ; and 3 ) a larger measure of K+ is adsorbed as outer-sphere composites in the i?? bed, ensuing double-layer compaction and a lessening in surface potencies.
Therefore, it was sensible to impute most of the decrease in carbamazepine surface assimilation to both its lower solubility and the higher ionisation of the silicon oxide surfaces. Indeed, lower carbamazepine solubility may prefer collection among carbamazepine molecules through hydrophobic interactions ( Turku et al. , 2007 ) , which potentially makes carbamazepine difficult to entree and adsorb in the silicon oxide pores. Additionally, the higher ionisation of the silicon oxide surfaces implies that a smaller figure of silanols remain, which are presumptively responsible for the surface assimilation of carbamazepine ( Bui and Choi, 2009 ) , and accordingly surface assimilation decreased.
Besides, the addition of ketoprofen surface assimilation can be attributed to double-layer compaction and a lessening of surface potencies ; more negatively charged Orudis molecules could adsorb to the surface due to the decrease of anion repulsive force.
3.2. Consequence of anions
Since the concentration of anions such as nitrate, hydrogen carbonate, sulphate, phosphate, and silicate in surface H2O is normally less than 1 millimeter ( Hem, 1985 ) , 1 millimeter anion solutions were used in these experiments. The pharmaceutical surface assimilation in the presence of different anions was so investigated and compared to surface assimilation in the presence of chloride ions ( see Fig.
S1, SI ) . Subsequent ANOVA trial consequences indicate that the tried anions did non significantly impact ( P & gt ; 0.05 ) surface assimilation of these pharmaceuticals to silica, as compared to chloride ions. This consequence can be attributed to the minimum surface assimilation of anions to silica surfaces, likely due to the electrostatic repulsive force between the negatively charged silicon oxide surface and anions.
3.3. Consequence of divalent cations
The surface assimilation of pharmaceuticals in the presence of bivalent cations ( Ca2+ , Mg2+ ) was compared to surface assimilation in the presence of monovalent K ions ( see Table S1, SI ) , with a sum-up of the consequences of the ANOVA trial shown in Table 2. The consequences suggest that bivalent cations did non significantly impact the surface assimilation of carbamazepine and diclofenac.
However, bivalent cations at low concentrations ( 1 millimeter ) were found to significantly impact the surface assimilation of isobutylphenyl propionic acid ( both Ca2+ and Mg2+ ) and Orudis ( merely Mg2+ ) , as the per centum of isobutylphenyl propionic acid and Orudis adsorbed was higher in 1 millimeter of divalent cations than that in K ions ( Table S1 ) . Pils and Laird ( 2007 ) besides reported that the sorption of Achromycin and Aureomycin at pH 7 was higher on Ca-saturated dirt constituents than on K-saturated dirt constituents. The ascertained impacts can be consequences of the surface assimilation of bivalent cations onto the silica surface. Below pH 7.5, divalent cations are physically adsorbed into the interface as counterions in topographic point of K ions to organize an outer-sphere complex i‚?SiO-aˆ¦M2+ ( Tadros and Lyklema, 1969 ) . And at low concentrations ( 1 millimeter ) , Ca2+ and Mg2+ are sorbed on silicon oxide to a greater extent than monovalent K+ ( Tadros and Lyklema, 1969 ) , which decreases the surface charge of silicon oxide, as compared to monovalent ions ( Persello, 2000 ) . Additionally, bivalent cations are able to bridge between negative charge sites on silicon oxide surfaces and the negative charge of pharmaceuticals ( Goyne et al. , 2005 ; Pils and Laird, 2007 ) ; conversely, monovalent K+ can merely fulfill one negative charge site at a clip.
Consequently, Orudiss and isobutylphenyl propionic acid, most of which are negatively charged in the media, are more favourable for surface assimilation on silicon oxide surfaces.Consequently, high concentrations ( 5 millimeter ) of divalent cations were expected to incur a higher addition of pharmaceutical surface assimilation than monovalent K+ . However, it was found that bivalent cations at high concentration did non significantly affect the surface assimilation of pharmaceuticals ( Table 2 ) except that the presence of 5 millimeter of Mg2+ facilitated a important lessening in ibuprofen surface assimilation ( Table S1 ) , compared to when K+ was present. The indistinctive surface assimilation of pharmaceuticals in the presence of bivalent cations and K+ suggests that the surface assimilation of both types of cations on silicon oxide surfaces reach a limited value and go equal, which can be a consequence of the low surface charge of silicon oxide ( Persello, 2000 ) . However, it is non good understood why the surface assimilation of isobutylphenyl propionic acid was reduced in the presence of 5 millimeter of Mg2+ .The undistinguished impacts of bivalent cations to the surface assimilation of diclofenac and carbamazepine are sooner discussed in the following subdivision.
3.4. Consequence of trivalent cations
In comparing with bivalent cations, trivalent cations ( Al3+ and Fe3+ ) displayed a more intense influence on pharmaceutical surface assimilation ( Fig. 2 ) despite holding a 10-50 times smaller concentration. Again, the ANOVA trial consequences ( Table 2 ) indicate that the surface assimilation of carbamazepine was non affected by the presence of trivalent cations, though the trivalent cations caused a important impact on the surface assimilation of diclofenac, isobutylphenyl propionic acid, and Orudis. Furthermore, whereas the presence of Fe3+ resulted in a alone addition in the surface assimilation of Orudis ( 10.
6 % ) , the presence of Al3+ enhanced the surface assimilation of diclofenac ( 17.6 % ) , isobutylphenyl propionic acid ( 13.3 % ) , and Orudis ( 18.
6 % ) ( Fig. 2 ) . Meanwhile, the clean experiments ( without silicon oxide ) revealed that merely in the presence of trivalent cations was there no alteration in pharmaceutical concentrations. These consequences are in understanding with old studies ( Westerhoff et al. , 2005 ; Vieno et al. , 2007 ) .
Therefore, the sweetening of pharmaceutical surface assimilation might be due to the surface assimilation of trivalent cations onto silicon oxide surfaces ( Persello, 2000 ) and/or the formation of composites between trivalent cations and the pharmaceuticals ( Wang et al. , 2008 ) .It is known that Al3+ and Fe3+ chiefly adsorb as an inner-sphere coordination composite at the silicon oxide surface ( Persello, 2000 ) , organizing positively charged surface groups ( Houston et al. , 2008 ) and ensuing in a lower surface potency. Furthermore, the specific surface assimilation of trivalent cations on the silicon oxide surface is able to change by reversal the cataphoretic charge ( Wakatsuki et al. , 1974 ) .
As a consequence, the silicon oxide surface becomes more active towards negatively charged acidic pharmaceuticals. Furthermore, it was reported that Cipro can organize composites with both surface metal species ( Al, Fe ) and besides with dissolved metal cations via the coordination of carboxylate and/or keto groups ( Gu and Karthikeyan, 2005b ; Trivedi and Vasudevan, 2007 ) . Hence, the three acidic pharmaceuticals ( diclofenac, isobutylphenyl propionic acid, and Orudis ) incorporating carboxylate groups may organize composites with both Al3+ and Fe3+ adsorbed on the silicon oxide surface and besides Al3+ and Fe3+ in the aqueous solution. Obviously, the formation of surface complexation between pharmaceuticals and adsorbed trivalent metals would heighten surface assimilation of the pharmaceuticals. In add-on, Wang et Al.
( 2008 ) reported that the surface assimilation of Achromycin on dirt increased in the presence of Cu ( II ) , which was partly attributed to the formation of water-soluble composites between Achromycin and Cu ( II ) . Consequently, composites formed between dissolved Al3+ and Fe3+ and the acidic pharmaceuticals would hold less negative charge and therefore are easy adsorbed on negatively charged surfaces of silicon oxide, instead than the pharmaceutical itself, thereby taking an addition in the surface assimilation of pharmaceuticals.Ketoprofen, which contains both keto and carboxylate groups ( see Table 1 ) , may hold a higher complexing affinity to Fe ( III ) ( both surface and aqueous species ) than the other acidic pharmaceuticals, perchance explicating why the presence of Fe3+ merely significantly increases ketoprofen surface assimilation ( Table 2 ) . The tabular array besides shows that among the trivalent cations, a perchance stronger surface assimilation of Al3+ to the silica surface produces singular alterations and a lower surface potency, compared with Fe3+ ( Wakatsuki et al. , 1974 ; Persello, 2000 ) , ensuing in a more important impact to the surface assimilation of diclofenac and isobutylphenyl propionic acid.Neither divalent ( Ca2+ , Mg2+ ) nor trivalent ( Al3+ , Fe3+ ) cations impacted the surface assimilation of carbamazepine ( Table 2 ) . These consequences can be attributed to the fact that the surface assimilation of impersonal carbamazepine is non affected by alterations in the silicon oxide surface charge in the instances.
To this terminal, it was antecedently proposed that the surface assimilation of carbamazepine is chiefly responsible by the formation of H bonding between silicon oxide surfaces and carbamazepine ( Bui and Choi, 2009 ) .The surface assimilation of diclofenac was merely influenced by the presence of Al3+ ( Table 2 ) , while other factors including ionic strength, alkaline-earth cations, and Fe3+ did non do any impact. This consequence indicates that Al3+ could strongly adsorb onto the silica surface to intensely change the surface features or that Al3+ can organize a stronger complex with diclofenac. Another possible account stems from the desorption consequences of the pharmaceuticals in a pH 7 buffer ( Bui and Choi, 2009 ) , in which the per centum of desorption followed the order: diclofenac ( ca. 20 % ) & lt ; carbamazepine & lt ; ibuprofen & lt ; Orudis. The lower desorption per centum of diclofenac suggests that a larger fraction of diclofenac is “ nonlabile ” adsorbed on silicon oxide, compared to the other pharmaceuticals.
This nonlabile adsorbed fraction appears to be largely unaffected by H2O features, explicating why the surface assimilation of diclofenac was non significantly influenced by factors other than Al3+ .
3.5. Consequence of natural organic affairs
The per centum of surface assimilation of four pharmaceuticals in the presence of NOM were investigated and compared with the controls ( Table S2, SI ) . The ANOVA trial consequences ( Table 3 ) indicate that NOM did non do any statistically important alteration in the surface assimilation of diclofenac on silicon oxide. Suwannee River HA entirely affected the surface assimilation of isobutylphenyl propionic acid, whereas Suwannee River FA significantly affected the surface assimilation of Orudis and isobutylphenyl propionic acid. In add-on, Suwannee River NOM significantly influenced the surface assimilation of carbamazepine, isobutylphenyl propionic acid, and Orudis.
Furthermore, the surface assimilation of pharmaceuticals was significantly decreased ( Table S2 ) by the impact of NOM ; a important impact was besides observed on the rejection of every pharmaceuticals in the presence of Suwannee River NOM ( Comerton et al. , 2009 ) . Our preliminary experiments showed that the surface assimilation of NOM on silicon oxide was negligible, which could be a consequence of the negatively charged NOM interacting with the high hydrophilicity and negative charge of the silicon oxide surfaces ( Yang et al.
, 2009 ) . Hence, the lessening of pharmaceutical surface assimilation could be attributed to an association among pharmaceuticals and NOM, which can be formed via hydrophobic interactions ( Kulshrestha et al. , 2004 ; Tulp et al. , 2009 ) and H bonding ( Gu et al. , 2007 ; Pils and Laird, 2007 ) . Such an association of pharmaceuticals with supramolecular humic substances would restrict the pharmaceuticals and accordingly diminish their surface assimilation on silicon oxide.The statistically undistinguished impact of NOM on the surface assimilation of diclofenac ( Table 3 ) may be due to the little sum of diclofenac in non-ionized signifier, compared to the remainder of the pharmaceuticals ( see Table 1 ) .
To this terminal, Tulp et Al. ( 2009 ) demonstrated that impersonal species sorbed to peat organic affair by a factor of ca. 40 times ( for isobutylphenyl propionic acid and Orudis ) higher than their corresponding anionic species, due to the negative charge of the organic affair.
The different impacts of assorted NOM on pharmaceutical surface assimilation could be dependent on the ability in doing an association between them, which in bend could be expected to depend on the hydrophobicity of both the pharmaceuticals and NOM ( see Table S3, SI ) . Sorption of both impersonal and anionic species to peat organic affair showed an addition with their hydrophobicity ( logKow ) ( Tulp et al. , 2009 ) . Owing to the isolation processs ( IHSS, 2008 ) , Suwannee River HA and Suwannee River FA contain merely hydrophobic organic acids, with HA by and large holding a higher hydrophobicity than FA ( Sutton and Sposito, 2005 ) , whereas Suwannee River NOM contains both hydrophobic and hydrophilic acids every bit good as other soluble organic solutes.
Note that the hydrophobicity of pharmaceuticals follows the order: isobutylphenyl propionic acid & gt ; ketoprofen & gt ; carbamazepine ( Table 1 ) . Therefore, it could be sensible to impute the alone impact of Suwannee River HA to ibuprofen surface assimilation ( Table 3 ) to the lucifer of hydrophobicity between isobutylphenyl propionic acid and HA ; this lucifer may take to organize a considerable interaction between them. Similarly, the lower hydrophobicity of FA potentially makes it suited to organize an association with both isobutylphenyl propionic acids and Orudis. Suwannee River NOM, which contains hydrophobic HA and FA, could seemingly interact with isobutylphenyl propionic acid and Orudis, thereby significantly impacting the surface assimilation of both ( Table 3 ) . The tabular array besides suggests that Suwannee River HA, Suwannee River FA, and therefore hydrophobic HA and FA in Suwannee River NOM may non organize considerable associations with carbamazepine, perchance due to the low hydrophobicity of carbamazepine. Hence, the impact of Suwannee River NOM to carbamazepine surface assimilation can be attributed to the association of the fraction of more hydrophilic acids and/or other soluble organic compounds ( proteins, saccharides, etc. ) with carbamazepine.
It is non yet clear why a higher concentration of Suwannee River HA and Suwannee River FA resulted in such an undistinguished impact on the surface assimilation of isobutylphenyl propionic acid to silica ( Table 3 ) .
The surface assimilation of carbamazepine, diclofenac, isobutylphenyl propionic acid, and ketoprofen on porous silicon oxide was investigated in the presence of different ionic strengths, anions, cations, and natural organic affair.
Whereas the presence of anions did non do any consequence on the surface assimilation of pharmaceuticals, additions in ionic strength and the presence of bivalent cations, trivalent cations, and NOM did significantly impact the surface assimilation of pharmaceuticals. The impact was found to be dependent on H2O features ( ionic strength, cations, NOM and their concentration ) and the belongingss of pharmaceuticals ( molecular charge, pKa, and hydrophobicity ) . As a consequence, this survey suggests that the surface assimilation of pharmaceuticals to silica in an aqueous environment can be strongly influenced by pharmaceutical belongingss, trivalent cations, every bit good as the solution pH ( Bui and Choi, 2009 ) ; furthermore, the influence of ionic strength, divalent cations, and NOM could non be neglected. In farther surveies, the effects of a combination of these factors will be investigated and more pharmaceuticals considered.