pH and ionic strength effects on the binding constant between a nitrogen-containing polycyclic aromatic compound and humic acid.

Polycyclic aromatic compounds (PACs) are widespread environmental pollutants with a high potential to act as human carcinogens and mutagens. The behavior of PACs is significantly affected by their interactions with dissolved organic matter (DOM), such as their transport, solubility, bioavailability, and bioaccumulation in the aquatic environment. Being a basic PAC, benzo(h)quinoline (BQ) is the dominant species, as the solution's pH value is higher than BQ's pK a (pK a of BQ = 4.2). In contrast, benzo(h)quinolinium (BQH(+)) is the major species, as the solution's pH value is lower than its pK a. The binding constant (K DOC), measured by fluorescence quenching, between BQ/BQH(+) and Leonardite humic acid (LHA) would decrease 70 to 95 % and 20 to 90 % when increasing the ionic strength in acidic and neutral to basic conditions, respectively. The results can be attributed to the added cation (Na(+) and Mg(2+)), which forms a bridge with LHA and enhances the intramolecular reaction among these functional groups, therefore inducing the coiling up within the LHA molecule. In addition, the decrease of the K DOC with added MgCl2/MgSO4 (75-95 %) is higher than that with added NaCl/Na2SO4 (20-75 %), indicating that the K DOC was affected by the charge density of cations. The fluorescence intensity of BQH(+) in the absence of LHA (F 0) was found to decay only in the acidic solution with Cl(-), suggesting that Cl(-) might be a heavy atom serving as a quencher in an acidic solution.

Complexation-flocculation combined with microwave-assisted headspace solid-phase microextraction in determining the binding constants of hydrophobic organic pollutants to dissolved humic substances.

The binding constants, KDOC, of selected polycyclic aromatic hydrocarbons (PAHs)-phenanthrene, anthracene, fluoranthene, and pyrene-to dissolved humic substances (DHS) were determined by complexation-flocculation combined with microwave-assisted headspace solid-phase microextraction (CF-MA-HS-SPME). The results obtained are comparable with KDOC data reported in the literature. No disruption of the PAH to DHS binding equilibrium was observed during the complexation-flocculation process. The present study, which is the first to determine KDOC by CF-MA-HS-SPME, provides an alternative approach to determine the KDOC of PAHs. CF-MA-HS-SPME provides some advantages over other methods, such as no limitation of fluorescent compounds, greater determination speed, and the capability of measuring various compounds simultaneously.

The role of the characteristics of humic substances in binding with benzo[h]quinoline.

The binding constants (K(DOC)) of the mixture of benzo[h]quinoline and its protonated analog, benzo[h]quinolinium, to four types of humic substances obtained from the International Humic Substances Society were determined by the fluorescence quenching method. A simple mixing model was used to eliminate the fluorescent interference from the minor analog in the solution and to deduce K(mix), which represents the overall binding as the sum of that for the individual analogs. The characteristics of humic substances, especially their hydrophobicity and aromaticity, established by principal component analysis of structural and elemental compositions, were the main determinants of the binding affinity with both benzo[h]quinoline and benzo[h]quinolinium (K(BQ) and K (BQH+) across a range of pH values. The strongest overall affinity of benzo[h]quinoline for humic substances is observed near pH 4 and with more hydrophobic humic substances, which suggests possible choices in attempts at remediation of benzo[h]quinoline containing particles with humic substances.

pH dependence of binding benzo[h]quinoline and humic acid and effects on fluorescence quenching.

The binding constant (K(DOC)) between humic acid and the nitrogen-containing polycyclic aromatic compound (N-PAC), benzo[h]quinoline, was measured at varying pH levels using fluorescence quenching (FQ). Because fluorescence characteristics of benzo[h]quinoline change with pH, determination required two optimum sets of excitation and emission wavelength pairs. A simple mixing model was used to eliminate the inherent fluorescence interference between benzo[h]quinoline and its protonated form, benzo[h]quinolinium, when estimating binding constants. Hydrophobic interaction is likely to control the binding between humic acid and benzo[h]quinoline and benzo[h]quinolinium, in lower and higher pH ranges (pH <3, pH >6). In contrast, cation exchange seems to control the binding affinity of benzo[h]quinolinium in the middle range of pH. The estimates of K(DOC) were up to 70% smaller after elimination of interference. This indicates that the contribution of the minor form influences estimates of the K(DOC)-pH trend for benzo[h]quinoline, and potentially explains the large discrepancy reported in the literature between results based on using FQ and those based on equilibrium dialysis methods. Previous FQ measurements overestimate K(DOC) at some pH values and lead to an underestimation of bioavailability in an aquatic environment. The application of our models appears to be necessary when using FQ for determining the K(DOC)-pH trend for organic compounds with acid-base pair analogs.

A preliminary assessment of polycyclic aromatic hydrocarbon distribution in the kenting coral reef waters of southern Taiwan.

This distribution and variation of 45 polycyclic aromatic hydrocarbons (PAHs) in the waters of Kenting coral reefs were investigated by using sensitive research-grade sampling and analytical methods. The concentration levels of total PAHs (including particulate and dissolved PAHs) in the Kenting waters were relatively low, ranging from 2.2 to 34.4 ng/L. There was no significant spatial difference in PAH concentrations among the sampling stations, even between the surface and bottom waters. The fraction of dissolved PAHs on average was greater than that of particulate PAHs due to the small amount of total suspended particles. The partition coefficients between the particulate and dissolved phase (log K(oc)) were positively correlated with their log K(ow) values (r(2) = 0.67, n = 80), except for the more hydrophobic PAHs with log K(ow) values greater than 5.91. Results of principal component analysis indicate that the patterns of particulate PAH compositions were similar through the Kenting waters in the fall and winter, whereas there was a significant spatial difference between the spring and summer samples, which might be affected by a combination of land runoff and coastal currents. PAHs along the Kenting coasts were dominated by low-molecular PAHs, which have higher solubility than high-molecular PAHs. Based on isomer ratios, analysis of the source of PAHs in the Kenting coastal waters demonstrated that the PAHs come mostly from petroleum and, to a lesser degree, from combustion.

Mixing of dissolved organic matter from distinct sources: using fluorescent pyrene as a probe.

Binary mixtures of humic substances (HSs) from three distinct sources (two soil humic acids and one natural organic matter) were used to investigate the mixing behavior of dissolved organic matters in the aquatic environment. Much longer time was required for equilibration of a solution of mixed HSs with pyrene as a probe, than for a solution comprising a single HS. Restructuring processes were responsible for the difference in equilibration kinetics and included conformational changes and aggregation. A major factor found controlling these processes was intermolecular interactions between components of HSs, although the concentration and hydrophobicity of the HSs were also important. In addition, the fluorescence quenching method yielded the binding constant (K DOC) of the HSs with pyrene. The K DOC of pyrene with binary humic mixtures was found to follow the conservative mixing rule. The findings of this study are applicable to studies of other hydrophobic organic pollutants and HSs and, will assist in modeling of the transport and fate of pollutants in aquatic environments.

Sources and distribution of polycyclic aromatic hydrocarbons in the sediments of Kaoping River and submarine canyon system, Taiwan.

In this study, we measured and analyzed polycyclic aromatic hydrocarbons (PAHs) in surface sediment samples collected from the Kaoping river and submarine canyon (KPSC) system to determine the compositional patterns and characteristic distributions of PAH and to elucidate the transport and fate of these land-derived particles. Concentrations of total PAH (sum of 28 PAH compounds) ranged from 22.6 to 45,100 ngg(-1) dry weight (dw) and the highest concentrations were found in the sediments of Donggang Harbor. The ratio of perylene to sum of penta-aromatic PAH isomers (47-55%) was higher in off-shore stations, suggesting a diagenetic PAH source. Various isomeric ratios also indicated that combustion was a significant source of PAH to the sediment at stations located along the Kaoping river and the north-western shelf of the Kaoping estuary. However, in the south-eastern shelf and some canyon sites, petroleum-derived PAHs were a more significant source of these compounds. Principal component analysis and hierarchical cluster analysis suggest PAHs in the sediments from the north-western shelf, and river and canyon sediments might be a pyrogenic product of coal and diesel-burning vehicles, while those of the south-eastern shelf may be petrogenic. PAH concentrations and compositional patterns are effective tracers of particulate transport in KPSC system. The seaward transport of riverine particulates was found to be mostly directed to NW-shelf and/or canyon.

Effects of ionic strength on the binding of phenanthrene and pyrene to humic substances: three-stage variation model.

This study compared the effects of ionic strength on the binding constants (K(doc)) of selected polycyclic aromatic hydrocarbons (PAHs) (phenanthrene and pyrene) and a terrestrial humic acid (Leonardite Humic Acid) in different electrolyte solutions (KCl, KBr, MgCl(2) and MgSO(4)). Distinct trends were found in K(doc) variation depending upon the range of ionic strength resulting from added electrolytes. These trends demonstrated similar shapes for all the systems studied, while degree of variation increased with hydrophobicity of the PAHs. Furthermore, different types of electrolytes had different effects on the interactions between humic acid (HA) and the PAHs. These differences were primarily caused by types of cation, not anion. To describe the complicated effects of ionic strength on K(doc), we developed a three-stage variation model that encompasses increasing and decreasing trends and plateaus in K(doc) associated with ionic strength, as well as the mechanisms behind these trends, including the variation of HA structure configuration, HA aggregation and the salting-out effect. This model illustrated the importance of sufficient experimental data when interpreting the influence of ionic strength on the trends in K(doc) variation.