Accumulation of humic-like and proteinaceous dissolved organic matter in zero-discharge aquaculture systems as revealed by fluorescence EEM spectroscopy.

Recirculating aquaculture systems (RAS), offering many economic and fish husbandry benefits, are characterized by an accumulation of dissolved organic matter (DOM) and, specifically, humic substances (HS). As reported in a number of studies, HS may affect biological activity in both invertebrates and vertebrates. Given the accumulation of HS in RAS, it is therefore of great interest to characterize DOM and, specifically, its HS fraction in the RAS. The present study was aimed at characterizing long-term changes in fluorescent DOM composition in the culture water of RAS systems, which were operated in a novel, zero water exchange mode. Two such zero-discharge recirculating systems (ZDS) were examined: a freshwater system, stocked with hybrid tilapia (Oreochromis aureus x Oreochromis niloticus) and a marine system, stocked with gilthead seabream (Sparus aurata). Excitation-emission matrices (EEMs) of fluorescence, coupled with parallel factor analysis (PARAFAC), were used to characterize and quantify the different DOM components in the ZDS. In the culture water, one tryptophan-like and four HS-like components were identified. The fluorescence intensities of three of the HS-like components as well as the tryptophan-like component increased at comparable rates during ZDS operation while a much slower accumulation of these compounds was observed in a parallel operated, flow-through, freshwater aquarium. The ZDS examined in this study comprised a sludge digestion stage where a considerable accumulation of all fluorescent components was detected. A HS-like components and a tryptophan-like component in blood of tilapia from the freshwater ZDS were similar to components found in the culture water. Blood levels of both components were higher in fish cultured in the DOM-rich ZDS than in fish raised in the control, flow-through freshwater aquarium. Fluorescence of the HS-like component found in the fish blood increased also with time of ZDS operation. The finding that fish blood contains a HS-like fluorescent component may have important implications for the understanding of the physiological effects of HS in fish and the possible benefits of these substances in aquaculture.

Hydration-assisted sorption of a probe organic compound at different Peat hydration levels: the link solvation model.

Sorption isotherms of phenol on Pahokee Peat as model natural organic matter(NOM) have been measured at different partial NOM hydrations (water activities). Sorption at a given phenol solution concentration is substantially smaller in the lower water activity systems than in higher water activity systems, reaching a sorption maximum at an intermediate water activity. Such cooperative phenol uptake at interim water activities as a result of NOM hydration (hydration-assisted sorption) is predicted by the link solvation model (LSM), whereby water enhances the disruption of the noncovalently cross-linked NOM structure, creating new sorption sites. The LSM is herein extended to account for the observed direct relationship between isotherm linearity and water activity. The extended LSM provides an excellent description of phenol sorption isotherm data at nine different NOM hydration levels with a single set of three unique parameters. The successful fit of the LSM supports the conceptual model of creation of new sorption sites for sorbate molecules in the hydrated organic matter sorbent, accompanied by competition for those new sites by water molecules at high water activities.

Competitive sorption of organic contaminants in chalk.

In the Negev desert, Israel, a chemical industrial complex is located over fractured Eocene chalk formations where transfer of water and solutes between fracture voids and matrix pores affects migration of contaminants in the fractures due to diffusion into the chalk matrix. This study tests sorption and sorption competition between contaminants in the chalk matrix to make it possible to evaluate the potential for contaminant attenuation during transport in fractures. Single solute sorption isotherms on chalk matrix material for five common contaminants (m-xylene, ametryn, 1,2-dichloroethane, phenanthrene, and 2,4,6-tribromophenol) were found to be nonlinear, as confirmed in plots of Kd versus initial solution concentration. Over the studied concentration ranges, m-xylene Kd varied by more than a factor of 100, ametryn Kd by a factor of 4, 1,2-dichloroethane Kd by more than a factor of 3, phenanthrene Kd by about a factor of 2, and 2,4,6-tribromophenol Kd by a factor of 10. It was earlier found that sorption is to the organic matter component of the chalk matrix and not to the mineral phases (Chemosphere 44 (2001) 1121). Nonlinear sorption isotherms indicate that there is at least some finite sorption domain. Bi-solute competition experiments with 2,4,6-tribromophenol as the competitor were designed to explore the nature of the finite sorption domain. All of the isotherms in the bi-solute experiments are more linear than in the single solute experiments, as confirmed by smaller variations in Kd as a function of initial solution concentration. For both m-xylene and ametryn, there is a small nonlinear component or domain that was apparently not susceptible to competition by 2,4,6-tribromophenol. The nonlinear sorption domain(s) is best expressed at low solution concentrations. Inert-solvent-normalized single and bi-solute sorption isotherms demonstrate that ametryn undergoes specific force interactions with the chalk sorbent. The volume percent of phenanthrene sorbed at the liquid solubility limit is calculated to be 13% v:v in both the single and bi-solute experiments. This value exceeds what may be reasonably interpreted as partitioning of phenanthrene into organic matter, despite the relative linearity of the phenanthrene sorption isotherm (compared with other compounds) in both single and bi-solute systems.

Temperature effect on carbachol-induced depression of spontaneous quantal transmitter release in frog neuromuscular junction.

The effects of carbachol (CCh) on the frequency (f) of the miniature endplate potentials were tested at temperatures between 5 and 30 degrees C. Higher CCh concentrations, 1 x 10(-5) and 5 x 10(-6) M, reduced the f to 60% and the temperature dependence was negligible. However, an inverse temperature dependence was found when low concentrations 3 x 10(-7) and 6 x 10(-7) M were applied. The depression of f was 40-50% in 5-10 degrees C but only 10-20% of the control in the 25 and 30 degrees C. During application of CCh, the new steady of f was reached at temperatures between 5 and 30 degrees C within 17-20 min (Q10 = 1.07). Much greater temperature dependence of recovery was observed during washing out CCh (Q10 = 1.6). The temperature-independence of the steady state effects of CCh, good agreement with Langmuir adsorption-desorption theory and non-steady kinetics indicate that physical rather than receptor-mediated events are responsible for the depression of f.

Suitability of dye-clay complexes for removal of non-ionic organic compounds from aqueous solutions.

Aqueous sorption of phenol, atrazine and naphthalene was measured on complexes formed from Na-montmorillonite (Fischer bentonite) and the organic cationic dyes crystal violet and rhodamine-B. Sorption isotherms were found to be non-linear. This agrees well with the rigid nature of the dye-clay organic coverage, which provides a finite surface for adsorption. High values of organic carbon-normalized distribution coefficients reached 20,000-25,000 for atrazine on rhodamine-B-montmorillonite, 7000 for atrazine on crystal violet-montmorillonite, and 1500 for phenol on crystal violet-montmorillonite. As such, dye-clays may significantly extend the variety of organoclay sorbents that effectively reduce aqueous concentrations of non-ionic organic compounds.

Sorption of organic contaminants in a fractured chalk formation.

Sorption capability of bedrock components from a fractured chalk province was evaluated using ametryn, phenanthrene, m-xylene, 2,4,6-tribromophenol, and 1,2-dichloroethane. Sorption isotherms for the four aromatic compounds were nonlinear on gray (unoxidized) chalk. Over the studied solution ranges, the distribution coefficient decreased by factor of 3 for phenanthrene and m-xylene, a factor 4 for ametryn, and by an order of magnitude for 2,4,6-tribromophenol. In contrast, 1,2-dichloroethane displayed a linear isotherm. The importance of polar interactions for ametryn sorption was evaluated by normalizing sorption to an "inert" solvent, n-hexane. n-Hexane-normalized sorption of ametryn was much greater than that of phenanthrene, presumably due to ametryn participation in hydrogen bonding interactions. In sharp contrast to sorption to gray chalk, sorption to white (oxidized) chalk is 100- to 1000-fold lower at any given solution concentration. The much greater sorption on gray chalk cannot be explained by specific surface area, clay content, or organic matter content; thus, the nature of the organic matter is considered to control sorption in the chalk samples. Gray chalk sorption capacity estimates for ametryn and 2,4,6-tribromophenol are similar, which, together with evidence of competition for sorption sites, suggests that the limited capacity sorption domain for both compounds is similar.

Solvation effect on organic compound interactions in soil organic matter.

We examine sorption of pyridine by soil organic matter (SOM) from different organic media including n-hexadecane, acetonitrile, acetone, and n-hexadecane mixtures with either acetonitrile or acetone and compare it with sorption from water. By using an activity-based comparison, we distinguish between solvent-assisted and solvent-competitive sorption behavior. Pyridine was selected because it forms strong complexes with phenolic and carboxylic groups, such that site interactions should dominate interactions in SOM. It is anticipated that pyridine sorption will be illustrative of the importance of disrupting strong interactions in a condensed, shrunken SOM phase for many organic compounds. It was generally found that activity-normalized pyridine uptake was assisted by polar solvent molecules rather than suppressed due to competition. An explanation is tendered on the basis of our earlier hypothesis of water-assisted disruption of polar SOM contacts. Certain polar moieties of dry SOM are unavailable for compound sorption due to strong interactions between them. By penetrating SOM structure, solvent molecules (and water) solvate (hydrate) polar moieties creating new sorption sites. Solvent molecules must solvate both moieties of the polar contact, such that the driving force for solvent-assisted sorption is solvation of the partner of the disrupted contact that does not directly interact with the sorbate.

Effect of chain length on interactions of aliphatic alcohols with suspended human serum albumin.

Enthalpy changes on the immersion of human serum albumin (HSA) into n-butanol, n-propanol, ethanol and methanol containing different amounts of water have been measured calorimetrically at 25 degrees C. Water sorption isotherms on HSA were also determined in water-n-butanol and water-ethanol mixtures. From comparison of the calorimetric and sorption data, it was concluded that there is a significant enthalpy change on the HSA immersion into methanol and ethanol even under conditions where there is no change in the quantity of adsorbed water. No similar contribution was found in the n-butanol based suspensions. Water monolayer capacity evaluated from the Langmuir model decreases also significantly when going from ethanol to n-butanol. Considering this non water sorption contribution, values of the monolayer capacity and the shape of the experimental dependences, it was inferred that a relatively small change of the solvent molecule structure (from n-propanol to ethanol) affects strongly the interactions of the protein with the solvent.