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PubMed2005

Thermal fluorescence quenching properties of dissolved organic matter.

The fluorescence excitation-emission matrices of dissolved organic matter (DOM) are investigated between 10 and 45 degrees C for river and waste waters and organic matter standards. With increased temperature, fluorescence intensity is quenched. It is demonstrated that for a range of river and wastewater samples, that tryptophan-like fluorescence exhibits a greater range of quenching (between 20+/-4% and 35+/-5%) than fulvic-like fluorescence (19+/-4 to 26+/-3%) over this temperature range. Humic substance standards exhibit similar fulvic-like (23+/-4%) fluorescence thermal quenching properties to river water samples (23+/-3%); however none of the samples exhibit quenching of tryptophan-like fluorescence to the same extent as the tryptophan standards (approximately 50%). Thermal fluorescence quenching is related to the exposure of the fluorophores to the heat source; our findings suggest that the tryptophan-like groups within DOM is more exposed in untreated wastewaters than in treated wastewaters riverine DOM. Thermal fluorescence properties have the potential to be used to source DOM, to provide additional chemical structural information, to temperature correct laser-induced remotely sensed DOM fluorescence, and to characterise DOM through the wastewater treatment process.

Fluorescence↗

PubMed2005

Enhancing spawning in the grey mullet (Mugil cephalus) by removal of dopaminergic inhibition.

A dot-blot immunoassay for the detection of vitellogenin (Vtg) in plasma of adult grey mullet (Mugil cephalus) was developed. The assay identified the sex of the tested fish prior to detectable gonadal development, enabling the establishment of broodstock at the desired ratio of 7:4 females to males. This broodstock was maintained under natural photoperiod, and used to study the relative effect of gonadotropin-releasing hormone (GnRH) and dopamine antagonists on oocyte maturation and ovulation, as well as the effect of 17alpha-methyltestosterone (MT) on spermiation. Three groups of females were treated with: (i) a single injection of dopamine antagonist, domperidone (Dom), (ii) GnRH analog (GnRHa) administered via ethylene-vinyl acetate copolymer (EVAc) slow-release implants or (iii) a combination of both Dom and GnRHa. Males were treated with MT, administered via EVAc slow-release implants. An additional group of untreated fish was used as a control. The Dom treatment proved to be more potent than the GnRHa treatment, and did not differ significantly from the combined treatment. The Dom and Dom+GnRHa treatments accelerated oocyte development and increased plasma estradiol levels equally, whereas the GnRHa treatment did not vary significantly from the control. MT was found to be a potent spermiating agent, which enhanced steady milt production in all treated males. In contrast, no spontaneous spermiation occurred in untreated males. Plasma 11-ketotestosterone (11-KT) levels were significantly higher in MT-treated males than in the controls. Interestingly, MT-treated males held with the GnRHa+Dom-treated females showed higher levels of plasma 11-KT than those held with GnRHa-treated females, indicating an additive effect which is probably attributable to female pheromones. Fully mature females were induced to spawn by injecting GnRHa alone or coupled with metaclopramide (a dopamine D2 receptors antagonist). The combined treatment, which included a dopamine antagonist, was found to be more potent in inducing ovulation and spawning as compared to GnRHa alone. In conclusion, our data suggest that dopaminergic inhibition is a major barrier along the reproductive axis that arrests spontaneous spawning in captive mullets.

Animals↗

PubMed2001

Interaction between Hg(II) and natural dissolved organic matter: a fluorescence spectroscopy based study.

Interaction between Hg(II) and dissolved organic matter (DOM) collected from surface water samples of the Florida Everglades was studied using different fluorescence spectroscopic methods. Complexation between Hg(II) and DOM leached from mangrove leaves, sawgrass, and periphyton was investigated. Both fluorescence emission and synchronous fluorescence spectra showed that these dissolved organic materials, whether they are highly degraded or are freshly leached, can "complex" Hg(II) since fluorescence intensity was quenched upon addition of Hg(II) to the DOM samples. Synchronous fluorescence spectra disclosed structural information on the DOM sample, regarding possible binding sites for Hg(II). Chemical parameters on the complexation of Hg(II), including the conditional stability constants and the percentage of fluorophores participating in the complexation, were estimated by the modified Stern-Volmer equation. A detailed investigation under different experimental conditions showed that the complexation of the DOM samples collected from the Everglades was influenced by pH, Cl-(aq) anion, and cations such as Ca2+ and Mg2+. Experimental results suggest that DOM-Hg(II) complexes can be removed from the water column through adsorption on biogenically precipitated CaCO3(s).

Florida↗

PubMed2002

Effect of alum treatment on the trihalomethane formation and bacterial regrowth potential of natural and synthetic waters.

Waters from five reservoirs and "synthetic waters", prepared using terrestrially derived dissolved organic matter (DOM) extracted from vegetation and reservoir catchment soils, were studied for their treatability with alum using a jar test procedure. DOM in drinking water is a precursor for the formation of trihalomethanes (THM) following chlorine disinfection and can also be a substrate for microbial growth in the drinking water distribution system. The trihalomethane formation potential (THMFP) represents an upper concentration limit on THMs formed by chlorination, while bacterial regrowth potential (BRP) is an indicator of the bioavailability of DOM. BRP and THMFP were measured before and after alum treatment and the results were related to the source of the DOM. It was found that freshly derived terrestrial DOM in synthetic water resulted in higher THMFP and BRP than DOM in reservoir waters. For the samples investigated, conventional alum treatment did not always reduce the THM precursor levels formed in laboratory tests below the NH&MRC (1996) guideline level of 250 microg/L nor produce microbially stable waters.

Alum Compounds↗

PubMed1999

The acute effects of monoamine reuptake inhibitors on the stimulus effects of hallucinogens.

In a previous study it was observed that fluoxetine potentiates the stimulus effects of lysergic acid diethylamide (LSD). In the present investigation, stimulus control was established in groups of rats using as training drugs the hallucinogens lysergic acid diethylamide (LSD); 0.1 mg/kg), (-)-2,5-dimethoxy-4-methylamphetamine [(-)-DOM; 0.56 mg/kg], ibogaine (10 mg/kg), and 5-methoxy-N,N-dimethyltryptamine (5-MeO-DMT; 3 mg/kg). A two-lever, fixed-ratio 10, positively reinforced task with saline controls was employed. The hypotheses tested were that (a) monoamine uptake inhibitors other than fluoxetine potentiate the discriminative effects of LSD, and (b) hallucinogens other than LSD are potentiated by acute pretreatment with monoamine uptake inhibitors. The effects of a range of doses of each of the training drugs were determined both alone and following pretreatment with the monoamine reuptake inhibitors fluoxetine, fluvoxamine, and venlafaxine. In LSD-trained subjects, all three reuptake inhibitors caused a significant increase in LSD-appropriate responding. Similar results were observed in rats trained with (-)-DOM and with ibogaine. In 5-MeO-DMT-trained subjects, only fluoxetine resulted in an enhancement of drug-appropriate responding. The reuptake inhibitors given alone elicited varying degrees of responses appropriate for the respective training drugs. For fluoxetine in rats trained with LSD and ibogaine, for venlafaxine in LSD trained, and for fluvoxamine in (-)-DOM trained, the degree of responding met our criterion for intermediate responding, i.e., significantly different from both training conditions. Subsequent experiments in (-)-DOM-trained subjects examined a range of doses of each of the reuptake inhibitors in combination with a fixed dose of (-)-DOM (0.1 mg/kg), which alone yielded about 50% (-)-DOM-appropriate responding. With the exception of the point obtained with the highest dose of venlafaxine, all data were compatible with additivity of effects rather than true potentiation. In summary, the present data extend our previous observation of the augmentation of the stimulus effects of LSD by fluoxetine to include other hallucinogens. The mechanisms by which these interactions arise and possible differential effects of acute and chronic treatment remain to be established.

Adrenergic Uptake Inhibitors↗

PubMed2000

Delayed onset muscle soreness: effect of an ischaemic block upon mechanical allodynia in humans.

The current study, for which ethical approval was obtained, was designed to assess the extent to which the tenderness or mechanical allodynia observed in delayed onset muscle soreness (DOMS) might be mediated by large diameter myelinated nerve fibres. Healthy human volunteers were recruited and randomly allocated to one of three groups: Normal-Control, Ischaemic-Control, and Test-DOMS (total n=21; n=7 in each group). In the Normal-Control group, subjects attended on a single occasion for assessment of mechanical pain threshold (MPT) at standardized sites over the biceps brachii using a pressure algometer for a period of 20 min. In both remaining groups, ischaemia was induced in subjects' non-dominant upper limbs by elevation of the limb, followed by application of a sphygmomanometer cuff at a pressure of 250 mmHg. Throughout the period of the block (20-40 min), sharp/blunt sensation was assessed at regular intervals. MPT was assessed upon inflation of the cuff and reassessed at 10 min intervals until deflation. In the two ischaemic block groups, current level of pain was also monitored using a computerized visual analogue scale (VAS) at the beginning and end of the procedure. Subjects in the Test-DOMS group attended 48 h prior to ischaemic block for induction of DOMS using a standardized regime of eccentric exercise, but thereafter were treated in exactly the same manner as the Ischaemic-Control group. Results showed a significant (P<0.05; ANOVA) increase in MPT in the Test-DOMS group by the 20 min point, corresponding to a 'normalization' of MPT; loss of the ability to distinguish between sharp/blunt sensation accompanied such changes. Parallel increases in reported pain were seen in both groups undergoing ischaemic block, indicating that the procedure did not alter nociception. While not definitive, these results suggest that altered processing of activity in large diameter (myelinated) afferents might underlie the mechanical allodynia observed in DOMS; thus, this is an area which warrants further investigation.

Adolescent↗

PubMedDate not supplied

Comparative behavioural toxicity of domoic acid and kainic acid in neonatal rats.

Cumulative behavioural toxicity was measured in groups of male and female rat pups (n=6/sex) at different stages of postnatal development. Dose-response curves (DRCs) for toxicity produced by domoic acid (DOM) were generated using animals on postnatal days (PND) 0, 5, 14, and 22, using a behavioural rating scale. In a subsequent experiment, DRCs for toxicity generated by either DOM or kainic acid were produced in rats at PND 8 and 14 for comparison between the two toxins. DOM was found to be a very potent neurotoxin in newborn rats and the potency of DOM progressively decreased with increasing age (interpolated ED(50)=0.12, 0.15, 0.30, and 1.06 mg/kg at PND 0, 5, 14, and 22, respectively). In addition, the patterns of behavioural expression were found to differ with age. Comparisons between DOM and kainic acid revealed that DOM was approximately six-fold more potent than kainate at both PND 8 and PND 14 and that both toxins were approximately two-fold less potent in PND 14 rats, compared to PND 8. This implies that the mechanism(s) responsible for reduced potency is/are similar between the two compounds. Consistent with previous reports, however, there were both similarities and differences in the observed patterns of behavioural toxicity produced by the two toxins at both ages.

Animals↗

PubMed2006

Passive sampler for dissolved organic matter in freshwater environments.

A passive sampler for the isolation of dissolved organic matter (DOM) from freshwater environments is described. The sampler consists of a molecular weight selective membrane (1000 kDa) and an anion exchange resin (diethylaminoethylcellulose (DEAE-cellulose)). NMR indicates the samplers isolate DOM that is nearly indistinguishable from that isolated using the batch DEAE-cellulose procedure. In a comparative study DOM isolated from Lake Ontario cost approximately 0.30 dollars/mg to isolate using the passive samplers while DOM isolated using the traditional batch procedure cost approximately 8-10 dollars/mg. The samplers have been shown to be effective in a range of freshwater environments including a large inland lake (Lake Ontario), fast flowing tributary, and wetland. Large amounts (gram quantities of DOM) can be easily isolated by increasing the size or number of samplers deployed. Samplers are easy to construct, negate the need for pressure filtering, and also permit a range of temporal and spatial experiments that would be very difficult or impossible to perform using conventional approaches. For example, DOM can be monitored on a regular basis at numerous different locations, or samplers could be set at different depths in large lakes. Furthermore, they could potentially be deployed into hard to reach environments such as wells, groundwater aquifers, etc., and as they are easy to use, they can be mailed to colleagues or included with expeditions going to difficult to reach places such as the Arctic and Antarctic.

Journal Article↗

PubMed2026

Ecological Restoration of the Soil-Like Function in the Bauxite Residue: Natural Microbiomes Mediated Molecular Transformation of Dissolved Organic Matter.

Soilization of bauxite residues offers a scalable route for long-term carbon management and ecological restoration. However, the microbial processes that transform exogenous organic inputs into stable soil-like carbon pools remain poorly resolved. Here, we combined cross-ecosystem meta-analysis, machine-learning prediction, native synthetic community (SynCom) construction, 13C-labeled straw microcosms, field validation, Fourier transform ion cyclotron resonance mass spectrometry, and genome-resolved metagenomics to unravel microbiome-mediated carbon transformation at the dissolved organic matter (DOM) molecular scale. Our meta-analysis revealed that alkaline industrial wastes retained soil-like DOM signatures but were enriched in microbial humic- and protein-like components, indicating active yet incomplete carbon processing. Guided by these patterns, native SynCom inoculation increased 13C incorporation into total organic carbon (TOC) and dissolved organic carbon (DOC), enlarged biodegradable and adsorbable DOC fractions, and shifted DOM from recalcitrant aromatic pools toward oxygenated carbohydrate-, tannin-, and phenolic-like molecular classes. Genome-resolved analyses linked this transformation to complementary polymer degradation and nutrient-cycling functions across fungal and bacterial guilds, including enriched carbohydrate-active enzymes in straw-carbon-utilizing metagenome-assembled genomes. Null model and thermodynamic analyses further showed that microbial communities were constrained by homogeneous selection, whereas DOM molecules were diversified through variable selection and redox-dependent transformation. Field-scale validation confirmed that SynCom promoted TOC and DOC accumulation and humic-like, high-density DOM fractions under alkaline conditions. Together, these findings establish a mechanistic framework in which functional microbiomes couple plant carbon depolymerization, DOM molecular diversification, and mineral-interactive carbon stabilization, providing a microbiome-guided strategy for carbon sequestration and soilization in the bauxite residue.

Soil↗

PubMed2001

Nature and chlorine reactivity of organic constituents from reclaimed water in groundwater, Los Angeles County, California.

The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.

Amino Acids↗

PubMed2001

Nature and transformation of dissolved organic matter in treatment wetlands.

This investigation into the occurrence, character, and transformation of dissolved organic matter (DOM) in treatment wetlands in the western United States shows that (i) the nature of DOM in the source water has a major influence on transformations that occur during treatment, (ii) the climate factors have a secondary effect on transformations, (iii) the wetlands receiving treated wastewater can produce a net increase in DOM, and (iv) the hierarchical analytical approach used in this study can measure the subtle DOM transformations that occur. As wastewater treatment plant effluent passes through treatment wetlands, the DOM undergoes transformation to become more aromatic and oxygenated. Autochthonous sources are contributed to the DOM, the nature of which is governed by the developmental stage of the wetland system as well as vegetation patterns. Concentrations of specific wastewater-derived organic contaminants such as linear alkylbenzene sulfonate, caffeine, and ethylenediaminetetraacetic acid were significantly attenuated by wetland treatment and were not contributed by internal loading.

Biodegradation, Environmental↗

PubMed2005

Indirect photolysis promoted by natural and engineered wetland water constituents: processes leading to alachlor degradation.

Wetland surface waters that received drainage from agricultural fields were probed for constituents that would promote the photodegradation of agriculture herbicides. Alachlor proved to be a good chemical probe for examining indirect photolysis due to its lack of reactivity by either direct photolysis or dark reaction pathways and its ubiquity as an agricultural herbicide. Water samples were taken from natural (Old Woman Creek) and engineered wetlands in Ohio that receive copious amounts of agricultural runoff. Possible photosensitizers including dissolved organic matter (DOM), iron, and nitrate were measured in the samples. In alkaline waters (pH > 7.8), the photochemical degradation of alachlor became important only in the presence of high nitrate levels (approximately equal to 1 mM). In pH-adjusted (approximately 4) samples, the observed degradation rate coefficient increased 3-18 times of that measured at the natural pH. Methanol quenching experiments and kinetics modeling suggest that hydroxyl radical is the principal reactant. The promotion of the reaction at the lower pH was apparently related to the activation of the photochemical pathways associated with the DOM and possibly iron-DOM complexes. The rate coefficients measured for the photodegradation of alachlor in reconstituted DOM isolates (cation-exchanged material with very low iron levels) were similar in magnitude to those measured in natural waters containing low amounts of nitrate and high amounts of DOM. Moreover, these reactions also exhibited a pH dependency. Thus, these results suggest that DOM plays a role in promoting an indirect photolytic mechanism that is highly pH dependent.

Acetamides↗

PubMed2004

Antimony(III) binding to humic substances: influence of pH and type of humic acid.

Conditional distribution coefficients (Dom) for Sb(III) binding to three commercial humic acids (terrestrial, coal, and aquatic) were measured at environmentally relevant Sb(III)/DOC ratios and as a function of pH using an equilibrium dialysis method. Maximum binding of Sb(III) was observed around pH 6 for two of the humic acids. The third humic acid showed constant Dom values up to pH 6 and decreasing Dom values for pH > 6. Sb(III)/DOC ratio was found to be important for Dom (20 times higher Dom for 60 times lower Sb(III)/DOC ratio). Moreover, Dom depends on the individual humic acid, suggesting that different functional groups are involved and/or different degrees of stabilization by chelation or H-bridges. Chemical modeling of Sb(III)-humics binding at different pH values is consistent with two binding sites involving (i) a phenolic entity forming a neutral complex and (ii) a carboxylic entity forming a negatively charged complex. Under environmentally relevant conditions, over 30% of total Sb(III) may be bound to natural organic matter.

Adsorption↗

PubMed2005

Comparison of the effects of sonolysis and gamma-radiolysis on dissolved organic matter.

The effects of 640 kHz sonolysis and 60Co gamma-radiolysis on dissolved organic matter (DOM) were compared through UV/ vis absorption spectrometric, dissolved organic carbon concentration ([DOC]), and potentiometric titration analyses. A reverse-phase chromatographic technique was used to compare changes in the DOM hydrophobicity distribution, and a size exclusion chromatographic technique with inline UV-A absorbance, fluorescence, and [DOC] detectors was used to compare changes in the DOM molecular weight distribution. Whereas upon radiolysis major decreases in absorbance and [DOC] were induced and near-total DOC removal was achieved, upon sonolysis there were major decreases in UV/vis absorbance but only minor decreases in [DOC], and a substantial quantity of hydrophilic nonchromophoric material remained in solution. In radiolysis, hydrophilic and hydrophobic DOM solution components were exposed to equal hydroxyl radical (*OH) concentrations. However, in sonolysis, hydrophobic DOM components were exposed to more elevated *OH concentrations than the hydrophilic components and consequently had enhanced rates of degradation. Sonolysis may be of interest in the design of advanced oxidation processes in which the selective elimination of hydrophobic solution components, such as hydrophobic organic contaminants and hydrophobic DOM domains into which they partition, is desired.

Carbon↗

PubMed2005

Efficient export of carbon to the deep ocean through dissolved organic matter.

Oceanic dissolved organic carbon (DOC) constitutes one of the largest pools of reduced carbon in the biosphere. Estimated DOC export from the surface ocean represents 20% of total organic carbon flux to the deep ocean, which constitutes a primary control on atmospheric carbon dioxide levels. DOC is the carbon component of dissolved organic matter (DOM) and an accurate quantification of DOM pools, fluxes and their controls is therefore critical to understanding oceanic carbon cycling. DOC export is directly coupled with dissolved organic nitrogen and phosphorus export. However, the C:N:P stoichiometry (by atoms) of DOM dynamics is poorly understood. Here we study the stoichiometry of the DOM pool and of DOM decomposition in continental shelf, continental slope and central ocean gyre environments. We find that DOM is remineralized and produced with a C:N:P stoichiometry of 199:20:1 that is substantially lower than for bulk pools (typically >775:54:1), but greater than for particulate organic matter (106:16:1--the Redfield ratio). Thus for a given mass of new N and P introduced into surface water, more DOC can be exported than would occur at the Redfield ratio. This may contribute to the excess respiration estimated to occur in the interior ocean. Our results place an explicit constraint on global carbon export and elemental balance via advective pathways.

Atmosphere↗

PubMed2000

Conformational transitions of the three recombinant domains of human serum albumin depending on pH.

Human serum albumin (HSA) is a protein of 66.5 kDa that is composed of three homologous domains, each of which displays specific structural and functional characteristics. HSA is known to undergo different pH-dependent structural transitions, the N-F and F-E transitions in the acid pH region and the N-B transition at slightly alkaline pH. In order to elucidate the structural behavior of the recombinant HSA domains as stand-alone proteins and to investigate the molecular and structural origins of the pH-induced conformational changes of the intact molecule, we have employed fluorescence and circular dichroic methods. Here we provide evidence that the loosening of the HSA structure in the N-F transition takes place primarily in HSA-DOM III and that HSA-DOM I undergoes a structural rearrangement with only minor changes in secondary structure, whereas HSA-DOM II transforms to a molten globule-like state as the pH is reduced. In the pH region of the N-B transition of HSA, HSA-DOM I and HSA-DOM II experience a tertiary structural isomerization, whereas with HSA-DOM III no alterations in tertiary structure are observed, as judged from near-UV CD and fluorescence measurements.

Humans↗

PubMed2006

Ascorbic acid supplementation does not attenuate post-exercise muscle soreness following muscle-damaging exercise but may delay the recovery process.

Exercise involving lengthening muscle actions, such as downhill running, results in delayed onset muscle soreness (DOMS), which may be attributable to reactive oxygen species (ROS). Although exercise causes oxidative stress, any link between ROS and DOMS remains speculative. There is emerging evidence to suggest that ROS play an important physiological role, assisting in the recovery process and protecting the cell from future damage; however, this has not been fully established. Despite this uncertainty as to the precise role of ROS, attempts to prevent post-exercise ROS production through antioxidant intervention are still common. The study investigated the effects of ascorbic acid supplementation on ROS production and DOMS following downhill running. Subjects were assigned to two groups. The ascorbic acid group (group AA) received 1 g ascorbic acid 2 h pre-, and for 14 d post-downhill running, whilst the placebo group (Pl group) received a placebo. Blood samples were drawn pre-supplement, pre- and post-exercise, and then 1, 2, 3, 4, 7 and 14 d post-exercise for analysis of ascorbate, malonaldehyde and total glutathione. DOMS was assessed using a visual analogue scale and pressure algometry. Muscle function was assessed using isokinetic dynamometry. Plasma ascorbate was elevated throughout in group AA compared with the Pl group. Downhill running resulted in DOMS in both groups. Muscle function was impaired post-exercise in both groups, although a delayed recovery was noted in group AA. Malonaldehyde increased 4 d post-exercise in the Pl group only. Ascorbic acid supplementation attenuates ROS production following downhill running, without affecting DOMS. Furthermore, ascorbic acid supplementation may inhibit the recovery of muscle function.

Adult↗

PubMed1992

Delayed onset muscle soreness: mechanisms and management.

This review describes the phenomenon of delayed onset muscle soreness (DOMS), concentrating upon the types of muscle contraction most likely to produce DOMS and the theories underlying the physiological mechanisms of DOMS. Ways of attempting to reduce the effects of DOMS are also summarized, including the application of physical and pharmacological therapies to reduce the effects of DOMS and training for reduction or prevention of DOMS.

Connective Tissue↗