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PubMed1992

Differential regulation of the nocturnal and diurnal prolactin surges in pregnant rats revealed by dopamine receptor antagonism.

We have explored temporal changes in the magnitude of dopamine (DA) interaction (DA tone) at the anterior pituitary lactotrophs related to both the nocturnal and diurnal prolactin (PRL) surges on day 8 of pregnancy, by utilizing a competitive DA D2 antagonist, domperidone (DOM). After withdrawal of blood from pregnant rats on day 7 in order to demonstrate the presence of a PRL surge, experimental rats received DOM (100 micrograms/kg i.v. or i.a.) at various times on day 8. Blood samples were taken immediately before and following injection of DOM at 5, 15, 30 and 60 min. The peak PRL response to DOM occurred 15 min after injection. Comparisons were made between circulating PRL levels immediately prior to and at several times following DOM administration for the various times of the day, and represented as incremental increases in PRL following DOM. During times on day 8 when PRL levels were normally low (24:00, 06:00, 12:00 and 16:00 h), pregnant rats exhibited a substantial PRL response to DOM. However, during the nocturnal PRL surge (02:00, 04:00 h) the peak PRL response to DOM was significantly lower. In sharp contrast, the PRL response to DOM administered during the diurnal PRL surge (18:00 h) was significantly higher than all other times of the day tested. In a dose-response study in which 10, 100 and 1,000 micrograms/kg DOM was administered at the two critical times when the response to DOM differed greatly, 02:00 and 18:00 h, there was a significantly reduced PRL response to DOM at 02:00 h compared to 18:00 h.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

PubMed2006

Variation in dissolved organic matter controls bacterial production and community composition.

An ongoing debate in ecology revolves around how species composition and ecosystem function are related. To address the mechanistic controls of this relationship, we manipulated the composition of dissolved organic matter (DOM) fed to aquatic bacteria to determine effects on both bacterial activity and community composition. Sites along terrestrial to aquatic flow paths were chosen to simulate movement of DOM through catchments, and DOM was fed to downslope and control bacterial communities. Bacterial production was measured, and DOM chemistry and bacterial community composition (using denaturing gradient gel electrophoresis of 16S rRNA genes) were characterized following incubations. Bacterial production, dissolved organic carbon (DOC)-specific bacterial production, and DOC consumption were greatest in mesocosms fed soil water DOM; soil water DOM enhanced lake and stream bacterial production by 320-670% relative to lake and stream controls. Stream DOM added to lake bacteria depressed bacterial production relative to lake controls in the early season (-78%) but not the mid-season experiment. Addition of upslope DOM to stream and lake bacterial communities resulted in significant changes in bacterial community composition relative to controls. In four of five DOM treatments, the bacterial community composition converged to the DOM source community regardless of the initial inoculum. These results demonstrate that shifts in the supply of natural DOM were followed by changes in both bacterial production and community composition, suggesting that changes in function are likely predicated on at least an initial change in the community composition. The results indicate that variation in DOM composition of soil and surface waters influences bacterial community dynamics and controls rates of carbon processing in set patterns across the landscape.

Alaska↗

PubMed2003

Delayed onset muscle soreness : treatment strategies and performance factors.

Delayed onset muscle soreness (DOMS) is a familiar experience for the elite or novice athlete. Symptoms can range from muscle tenderness to severe debilitating pain. The mechanisms, treatment strategies, and impact on athletic performance remain uncertain, despite the high incidence of DOMS. DOMS is most prevalent at the beginning of the sporting season when athletes are returning to training following a period of reduced activity. DOMS is also common when athletes are first introduced to certain types of activities regardless of the time of year. Eccentric activities induce micro-injury at a greater frequency and severity than other types of muscle actions. The intensity and duration of exercise are also important factors in DOMS onset. Up to six hypothesised theories have been proposed for the mechanism of DOMS, namely: lactic acid, muscle spasm, connective tissue damage, muscle damage, inflammation and the enzyme efflux theories. However, an integration of two or more theories is likely to explain muscle soreness. DOMS can affect athletic performance by causing a reduction in joint range of motion, shock attenuation and peak torque. Alterations in muscle sequencing and recruitment patterns may also occur, causing unaccustomed stress to be placed on muscle ligaments and tendons. These compensatory mechanisms may increase the risk of further injury if a premature return to sport is attempted.A number of treatment strategies have been introduced to help alleviate the severity of DOMS and to restore the maximal function of the muscles as rapidly as possible. Nonsteroidal anti-inflammatory drugs have demonstrated dosage-dependent effects that may also be influenced by the time of administration. Similarly, massage has shown varying results that may be attributed to the time of massage application and the type of massage technique used. Cryotherapy, stretching, homeopathy, ultrasound and electrical current modalities have demonstrated no effect on the alleviation of muscle soreness or other DOMS symptoms. Exercise is the most effective means of alleviating pain during DOMS, however the analgesic effect is also temporary. Athletes who must train on a daily basis should be encouraged to reduce the intensity and duration of exercise for 1-2 days following intense DOMS-inducing exercise. Alternatively, exercises targeting less affected body parts should be encouraged in order to allow the most affected muscle groups to recover. Eccentric exercises or novel activities should be introduced progressively over a period of 1 or 2 weeks at the beginning of, or during, the sporting season in order to reduce the level of physical impairment and/or training disruption. There are still many unanswered questions relating to DOMS, and many potential areas for future research.

Athletic Injuries↗

PubMed2000

Domoic acid-induced neurodegeneration resulting in memory loss is mediated by Ca2+ overload and inhibition of Ca2+ + calmodulin-stimulated adenylate cyclase in rat brain (review).

Domoic acid is a shellfish toxin which produces neurodegeneration and CNS dysfunction, notably a loss of short-term memory. This toxin was found in blue mussels (Mytilus edulis) cultivated in river water in the east coast of Prince Edward Island in Canada and caused human poisoning. The toxin was localized in the stomach of blue mussels, which was engorged with algae, Nitzschia pungens, that were filtered from the surrounding water. The toxin was isolated from contaminated mussels or phytoplankton, and identified chemically as domoic acid (DOM) which is a tricarboxylic amino acid. Due to its structural resemblance to glutamic, aspartic and kainic acids, DOM was considered to produce excitotoxicity by similar mechanism(s). However, the latest evidence indicates differences in its mode of action from these excitatory agonists. We propose that DOM induces toxicity via changes in intracellular concentration of Ca2+ ([Ca2+]i). Results of our studies demonstrate that DOM elevated [Ca2+]i in brain slices. Glucose deprivation and removal of Na+ from the Krebs-bicarbonate medium further elevated [Ca2+]i, suggesting a relationship between glucose metabolism (cell energy), Na+ and Ca2+ transfer across neuronal membrane. DOM-induced rise in [Ca2+]i was due to enhanced Ca2+ influx and its mobilization from the endoplasmic reticulum. In addition, diminished Ca2+-ATPase activity due to lack of ATP, and variable amounts and expression of calcium binding proteins (CaBP) appear to contribute to an elevation in [Ca2+]i in response to DOM. Most interestingly, DOM inhibited Ca2+ and calmodulin-stimulated adenylate cyclase activity in brain membranes, resulting in reduced level of cyclic AMP. Cyclic AMP is known to activate protein kinase A to enhance phosphorylation of Ca2+ channels, thereby, reducing Ca2+ influx to prevent the development of Ca2+ overload which is detrimental to neuronal cell function (neuroprotection). However, DOM reduced cyclic AMP level, diminishing the feedback control of cyclic AMP on Ca2+ influx via Ca2+ channels, thereby, allowing continuing enhanced Ca2+ influx, resulting in Ca2+ overload which adversely affects many intracellular processes to induce toxicity. Ca2+ and CaM-stimulated adenylate cyclase activity in brain is highly correlated with the acquisition and retention of memory in different organisms. Calcium binding proteins bind Ca2+ reversibly and provide intracellular Ca2+ buffering, thereby, protecting neuronal cell from damage by Ca2+ overload in response to DOM. DOM appears to interfere with the cross talk between Ca2+ and cyclic AMP which is necessary for neuronal cell function. We have also demonstrated that DOM stimulates GLU release from synaptosomes and may produce some of its toxic effects via excess GLU in the neuronal synapse. In conclusion, DOM-induced neurodegeneration resulting in a loss of memory is mediated by Ca2+ overload, inhibition of Ca2+ and CaM-stimulated adenylate cyclase activity, and/or by the enhanced GLU release in rat brain.

Adenylyl Cyclases↗

PubMed1986

Excretion profiles of the mycotoxin deoxynivalenol, following oral and intravenous administration to sheep.

The excretion profiles of deoxynivalenol (DON) and metabolites (DON glucuronide conjugate, 3 alpha, 7 alpha,15-trihydroxytrichothec-9,12-diene-8-one (DOM-1), and DOM-1 glucuronide conjugate) were defined in male sheep following either intravenous (iv) or oral administration of the toxin at levels of 0.5 and 5.0 mg DON/kg body wt, respectively. After iv dosing, urinary DON levels declined in a biphasic fashion with an average elimination half-life (terminal phase) of 1.2 hr, diminishing to baseline concentrations by 8 hr. Maximum urinary excretion rates for the two major metabolites identified (conjugated DON, conjugated DOM-1) occurred 0.5-1.5 hr after dosing, exhibiting elimination half-lives of 2.2 and 3.1 hr, respectively. Total recovery accounted for only about 66.5% of the dose: 63.0% in the urine (24.1% DON, 21.2% conjugated DON, 0.5% DOM-1, 17.2% conjugated DOM-1) and 3.5% in bile (made up almost completely of conjugated DOM-1). The peak biliary excretion rate for conjugated DOM-1 was found to occur within 1 hr postdosing, which rapidly declined to baseline levels by 5 hr. Following oral administration, urinary excretion rates of the major metabolites (DON, conjugated DON, conjugated DOM-1) reached maximum 6-9 hr post-treatment, and declined exponentially with t 1/2 values of 3.2, 4.0, and 5.0 hr, respectively. Urinary and biliary recovery of administered DON averaged approximately 7.1%: 7.0% in urine (2.1% DON, 3.6% conjugated DON, 0.06% DOM-1, 1.2% conjugated DOM-1) and 0.11% in bile (predominantly conjugated DOM-1).(ABSTRACT TRUNCATED AT 250 WORDS)

Administration, Oral↗

PubMed2006

Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene.

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.

Benzo(a)pyrene↗

PubMed2005

Mobilization of arsenic by dissolved organic matter from iron oxides, soils and sediments.

The arsenic contamination of aquifers has been linked to the input of dissolved organic matter (DOM). In light of this suggestion, the aim of this study was to quantify chemical effects of DOM on desorption and redox transformations of arsenic bound to synthetic iron oxide and natural samples from different geochemical environments (soils, shallow aquifer, lake sediment). In batch experiments, solutions containing 25-50 mg/L of two different types of DOM (purified peat humic acid and DOM from a peat drainage) were used as extractants in comparison to inorganic solutions. DOM solution was able to mobilize arsenic from all solid phases. Mobilization from iron oxides (maximum: 53.3%) was larger than from natural samples (maximum: 2.9%). The mobilization effect of extractants decreased in the order HCl>NaH2PO4>DOM>NaNO3. DOM solutions, therefore, mainly targeted weakly sorbed arsenic. Mobilization was complete within 24-36 h and DOM was sorbed during incubation indicating competition for sorption sites. The same patterns were observed for different DOM types and concentrations. Addition of DOM lead to (a) enhanced reduction (maximum 7.8%) and oxidation (6.4%) of arsenic in aqueous solution and (b) the appearance of arsenite in aqueous phase of soil samples (5.5%). As the primary mechanism for the arsenic release from solid phases we identified the competition between arsenic and organic anions for sorption sites, whereas redox reactions were probably of minor importance. The results of this study demonstrate that sorption of DOM has a strong potential to mobilize arsenic from soils and sediments.

Adsorption↗

PubMed2005

Adsorption of dissolved natural organic matter by modified activated carbons.

Adsorption of dissolved natural organic matter (DOM) by virgin and modified granular activated carbons (GACs) was studied. DOM samples were obtained from two water treatment plants before (i.e., raw water) and after coagulation/flocculation/sedimentation processes (i.e., treated water). A granular activated carbon (GAC) was modified by high temperature helium or ammonia treatment, or iron impregnation followed by high temperature ammonia treatment. Two activated carbon fibers (ACFs) were also used, with no modification, to examine the effect of carbon porosity on DOM adsorption. Size exclusion chromatography (SEC) and specific ultraviolet absorbance (SUVA(254)) were employed to characterize the DOMs before and after adsorption. Iron-impregnated (HDFe) and ammonia-treated (HDN) activated carbons showed significantly higher DOM uptakes than the virgin GAC. The enhanced DOM uptake by HDFe was due to the presence of iron species on the carbon surface. The higher uptake of HDN was attributed to the enlarged carbon pores and basic surface created during ammonia treatment. The SEC and SUVA(254) results showed no specific selectivity in the removal of different DOM components as a result of carbon modification. The removal of DOM from both raw and treated waters was negligible by ACF10, having 96% of its surface area in pores smaller than 1 nm. Small molecular weight (MW) DOM components were preferentially removed by ACF20H, having 33% of its surface area in 1--3 nm pores. DOM components with MWs larger than 1600, 2000, and 2700 Da of Charleston raw, Charleston-treated, and Spartanburg-treated waters, respectively, were excluded from the pores of ACF20H. In contrast to carbon fibers, DOM components from entire MW range were removed from waters by virgin and modified GACs.

Adsorption↗

PubMed2004

Binding of 2,4,6-trinitrotoluene, aniline, and nitrobenzene to dissolved and particulate soil organic matter.

The distribution of TNT* (the sum of TNT and its degradation products), aniline, and nitrobenzene between particulate organic matter (POM), dissolved soil organic matter (DOM), and free compound was studied in controlled kinetic (with and without irradiation) and equilibrium experiments with mixtures of POM and DOM reflecting natural situations in organic rich soils. The binding of TNT* to POM was fast, independent of irradiation, and adsorption isotherms had a great linear contribution (as determined by a mixed model), indicative of a hydrophobic partitioning mechanism. The binding of TNT* to DOM was slower, strongly enhanced under nonirradiated conditions, and adsorption isotherms were highly nonlinear, indicative of a specific interaction between TNT derivatives and functional groups of DOM. Nitrobenzene was associated to both POM and DOM via hydrophobic partitioning, whereas aniline binding was dominated by specific binding to POM and DOM functional groups. On the basis of nitrobenzene and TNT* adsorption parameters determined by a mixed Langmuir + linear model, POM had 2-3 times greater density of hydrophobic moieties as compared to DOM. This difference was reflected by a greater (O + N)/C atomic ratio for DOM. The sum of C-C and C-H moieties, as determined by X-ray photoelectron spectroscopy (XPS), and the sum of aryl-C and alkyl-C, as determined by solid-state cross-polarization magic-angle spinning (CP-MAS) 13C NMR, could only qualitatively account for differences in adsorption parameters. Aliphatic C was found to be more important for the hydrophobic partitioning than aromatic C. On the basis of nonlinear adsorption parameters,the density of functional groups reactive with aniline and TNT derivatives was 1.3-1.4 times greater in DOM than in POM, which was in fair agreement with 13C NMR and XPS data for the sum of carboxyl and carbonyl groups as potential sites for electrostatic and covalent bonding. We conclude that in contaminated soils characterized by continuous leaching of DOM, formation of TNT derivatives (via biotic and abiotic reductive degradation) and their preference for specific functional groups in DOM may contribute to a significant transportation of potentially toxic TNT compounds into surface waters and groundwaters.

Adsorption↗

PubMed2004

Photosensitized degradation of bisphenol A by dissolved organic matter.

The direct and indirect photolysis of bisphenol A (BPA) was investigated using a solar simulator in the absence and presence of dissolved organic matter (DOM). BPA degradation by direct photolysis was significantly slower than its rate in the presence of DOM. In natural waters, the direct photolytic pathway would be even less important due to light screening effects. Surprisingly, differences in the rate of indirect BPA photolysis were relatively small between DOM samples. Two of the DOM samples represented terrestrial (Suwannee River fulvic acid) and autochthonous (Lake Fryxell) geochemical endmembers. The third DOM (Fulton County, Ohio) was derived from a temperate artificial wetland. We were unable to correlate BPA photoreactivity to the structural components of DOM or its extinction coefficient at 280 nm. The addition of methanol, a hydroxyl radical scavenger, to reaction solutions slowed but did not completely quench the indirect photolysis of BPA. This observation suggests that BPA photodegrades via multiple pathways involving other transients formed by the photolysis of DOM. Competitive experiments using 2,4,6-trimethylphenol also reduce the reaction rate of BPA by DOM and implythat other DOM-derived phototransients (e.g., excited triplet state DOM) are involved in the reaction. The reaction rate coefficients reported under solar-simulated irradiance in the presence of DOM are significantly faster than those reported for the microbial degradation of BPA. Thus, in natural surface waters photosensitized transformation of BPA by dissolved organic matter may be as important as biodegradation.

Benzhydryl Compounds↗

PubMedDate not supplied

Binding of 2,4,6-trinitrotoluene and its degradation products in a soil organic matter two-phase system.

The widely used explosive 2,4,6-trinitrotoluene (TNT) and its degradation products are of large environmental concern because of their toxic properties and high concentrations encountered in contaminated soils. Batch experiments were used to study TNT* (the sum of TNT and its degradation products) bonding to dissolved (DOM) and particulate (POM) soil organic matter. Reversed-phase high performance liquid chromatography (RP-HPLC) was used as a separation technique in combination with 14C-labeled TNT to determine free TNT and TNT* bound to DOM. By use of dialysis we showed that DOM did not interfere with the HPLC analysis of free TNT. Depending on pH and total TNT concentration, the relative distribution of TNT* among water, POM, and DOM varied between 60 to 90, 10 to 30, and 0.5 to 6%, respectively, after 22 h of equilibration. The association of TNT* to DOM was strongly pH dependent and followed a nonlinear Langmuir isotherm. The association of TNT* to POM was less pH dependent and data were equally well fitted by linear and nonlinear isotherms. Particulate organic matter had 6.4 (pH 6.2) to 22 (pH 5.2) times greater capacity to bind TNT* than DOM, but the binding strength (the slope of the isotherm) was greater for DOM. The TNT degradation was enhanced with increasing concentration of soil organic matter, resulting in a stronger bonding of TNT* to DOM and POM. Based on our results, combined with other recent findings, we suggest that it is mainly the degradation products of TNT that associate with DOM and POM, and that the association with DOM is mainly of ionic character involving specific DOM sites. The greater binding capacity and a weaker, linear type of isotherm suggests a nonspecific type of partitioning in POM, possibly of hydrophobic character.

Biological Availability↗

PubMed1994

Evidence that 1-(2,5-dimethoxy-4-methylphenyl)-2-aminopropane-induced hypophagia and hyperthermia in rats is mediated by serotonin-2A receptors.

The administration of various doses of the phenylisopropylamine hallucinogen 1-(2,5-dimethoxy-4-methylphenyl)-2-aminopropane (DOM) to rats produced dose-related decreases in 1-hr food intake in a food-restricted paradigm and in locomotor activity. DOM also produced dose-related increases in temperature. Pretreatment with propranolol [a beta adrenoceptor antagonist that also has high binding affinity for serotonin (5-HT) 5-HT1A, 5-HT1B and 5-HT2C sites], bemesetron or ondansetron (5-HT3 antagonists) did not attenuate either DOM-induced hypophagia or hyperthermia. In contrast, pretreatment with metergoline (a 5-HT1/5-HT2 antagonist) and ritanserin (a 5-HT2A/5-HT2C antagonist) significantly attenuated both DOM-induced hypophagia and hyperthermia. However, pretreatment with mesulergine (a 5-HT2C/5-HT2A antagonist) significantly attenuated DOM-induced hyperthermia but not hypophagia. On the other hand, spiperone (5-HT1A/5-HT2A/D2 antagonist) pretreatment significantly attenuated DOM-induced hyperthermia but accentuated DOM-induced hypophagia. Daily administration of DOM (1.0 mg kg-1 day-1) produced complete tolerance to its hypophagic effect by day 4 but did not produce cross-tolerance to m-chlorophenylpiperazine-induced hypophagia. In contrast, daily administration of DOM for 7 days did not produce either tolerance to its hyperthermic effect or modify m-chlorophenylpiperazine-induced hyperthermia in rats. These findings suggest that DOM-induced hypophagia and hyperthermia in rats are mediated by stimulation of 5-HT2a receptors.

DOM 2,5-Dimethoxy-4-Methylamphetamine↗

PubMed2003

Experimental evidence that terrestrial carbon subsidies increase CO2 flux from lake ecosystems.

Subsidies are donor-controlled inputs of nutrients and energy that can affect ecosystem-level processes in a recipient environment. Lake ecosystems receive large inputs of terrestrial carbon (C) in the form of dissolved organic matter (DOM). DOM inputs may energetically subsidize heterotrophic bacteria and determine whether lakes function as sources or sinks of atmospheric CO(2). I experimentally tested this hypothesis using a series of mesocosm experiments in New England lakes. In the first experiment, I observed that CO(2) flux increased by 160% 4 days following a 1,000 microM C addition in the form of DOM. However, this response was relatively short lived, as there was no effect of DOM enrichment on CO(2) flux beyond 8 days. In a second experiment, I demonstrated that peak CO(2) flux from mesocosms in two lakes increased linearly over a broad DOM gradient (slope for both lakes=0.02+/-0.001 mM CO(2).m(-2) day(-1) per microM DOC, mean+/-SE). Concomitant changes in bacterial productivity and dissolved oxygen strengthen the inference that increasing CO(2) flux resulted from the metabolism of DOM. I conducted two additional studies to test whether DOM-correlated attributes were responsible for the observed change in plankton metabolism along the subsidy gradient. First, terrestrial DOM reduced light transmittance, but experimental shading revealed that this was not responsible for the observed patterns of CO(2) flux. Second, organically bound nitrogen (N) and phosphorus (P) accompanied DOM inputs, but experimental nutrient additions (without organic C) caused mesocosms to be saturated with CO(2). Together, these results suggest that C content of terrestrial DOM may be an important subsidy for freshwater bacteria that can influence whether recipient aquatic ecosystems are sources or sinks of atmospheric CO(2).

Carbon↗

PubMed2005

Dissolved organic matter in pore water of freshwater sediments: effects of separation procedure on quantity, quality and functionality.

Pore water was separated either with or without water extraction prior to centrifugation (7600 or 20,000 x g) in order to investigate the effects of separation procedure on the amount and properties of dissolved organic matter (DOM i.e. the material passing through a 0.45-microm filter) in three freshwater sediments. On the basis of solubility in alkaline, organic matter was concluded to compose of humic substances in two (S1 and S3) and of humin (S2) in one of the sediments. DOM in the samples was quantified by total organic carbon measurement. Specific UV-absorption (SUVA) and high performance size exclusion chromatography (HPSEC) analyses were used to characterize DOM. Sorption of pyrene was used as a measure for functionality of DOM. Both water extraction and centrifugation speed were shown to affect the properties of DOM; however, the effects were sediment dependent. Water extraction increased the amount of DOM separated from the two sediments that had humic character (S1 and S3). In most cases water extraction increased SUVA and shifted the molecular size distribution of DOM towards larger sizes. The separation procedure had also an effect on the functionality of DOM. In water extracted samples of S2 and S3 the sorption of pyrene was higher than in the corresponding samples separated without water extraction, whereas in S1 similar effect was not found. Generally, centrifugation speed had smaller effects on the properties of DOM than water extraction. The fact that the effects of separation procedure on DOM depend on the sediment characteristics complicates the comparison between samples and evaluation of functionality in field conditions.

Adsorption↗

PubMed2005

Evaluating spectroscopic and chromatographic techniques to resolve dissolved organic matter via end member mixing analysis.

Real-time or near real-time in-situ monitoring of dissolved organic matter (DOM) composition in natural waters and engineered treatment systems provides critical information to water quality scientists and engineers, particularly when the monitoring techniques can provide some information about the chemical nature of DOM. The efficacy of various indices derived from rapid, low-cost spectroscopic and chromatographic techniques to discriminate DOM composition was tested for samples prepared from well-defined mixtures of purified Aldrich humic acid (PAHA) and Suwannee River fulvic acid (SRFA). Sensitivities of the discrimination indices were examined by comparing (1) the differences between measured values and those predicted based from mass balance and the end member characteristics, and (2) the linear correlations between index values and mass ratios of the DOM mixtures. Size exclusion chromatography (SEC) results revealed that the weight-average molecular weight (MW(w)) may be a useful approach for tracking DOM mixing processes, although the number-average molecular weight (MW(n)) may be better for distinguishing different DOM compositions. Specific ultraviolet absorbance measured at 254 nm (SUVA(254)) performed better as a discrimination index than did two previously recommended absorbance ratios, both in terms of making better predictions of intermediate compositions and in exhibiting a more linear correlation with PAHA mass ratio. Several well-defined peaks in the derivative absorption spectra (301 and 314 nm for the first derivative, 217 nm for the third derivative, and 211 and 224 nm for the fourth derivative) also were found to be promising potential DOM discrimination indices. Finally, a fluorescence ratio based on humic- versus fulvic-like fluorescence proved to be a superior DOM discrimination index for the two DOM end members studied here. In general, this study illustrates the evaluation process that should be followed to develop rapid, low-cost discrimination indices to monitor DOM compositions based on end member mixing analyses.

Benzopyrans↗

PubMed2003

Solid-state and multidimensional solution-state NMR of solid phase extracted and ultrafiltered riverine dissolved organic matter.

In this study we used multidimensional solution-state NMR to elucidate the differences in the chemical composition of solid phase extracted and ultrafiltered DOM isolates. DOM was isolated from water sampled from an oligotrophic river, the River Tagliamento (Italy). The recovery of total DOM was up to 42% with both isolation techniques. In addition to 1- and 2-D solution-state NMR, we also applied 1-D solid-state 13C NMR spectroscopy for DOM characterization. 13C NMR spectroscopy only produced broad overlapping resonances, thus allowing a bulk characterization of DOM composition. However, it demonstrated that the bulk chemical composition of the two DOM fractions exhibited minor spatial-temporal changes. The 2-D experiments (TOCSY, HMQC) showed that the solid phase extracted hydrophobic DOM contained predominantly aliphatic esters, ethers, and hydroxyl groups, whereas the ultrafiltered DOM was comprised partially of peptides/protein, with further evidence for a small amount of aliphatic/fatty acid material. Sugars were present in both DOM fractions. The results show the two isolation techniques selected for different suites of compounds within the bulk DOM pool.

Environmental Monitoring↗

PubMed2003

Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter.

Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the > 10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation-emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation-emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (phi(i,n)). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet-visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 hydrophobic or hydrophilic acid, neutral, and base DOM fractions plus nonfractionated DOM from wastewater effluents and rivers in the southwestern United States. DOM fractions fluoresced in one or more EEM regions. The highest cumulative EEM volume (phi(T,n) = sigma phi(i,n)) was observed for hydrophobic neutral DOM fractions, followed by lower phi(T,n) values for hydrophobic acid, base, and hydrophilic acid DOM fractions, respectively. An extracted wastewater biomass DOM sample contained aromatic protein- and humic-like material and was characteristic of bacterial-soluble microbial products. Aromatic carbon and the presence of specific aromatic compounds (as indicated by solid-state 13C NMR and FTIR data) resulted in EEMs that aided in differentiating wastewater effluent DOM from drinking water DOM.

Biomass↗

PubMed2001

Effects of water hardness and dissolved organic material on bioavailability of selected organic chemicals.

The influence of water hardness and dissolved organic matter (DOM) on bioavailability of organic chemicals to Daphnia magna was studied by using benzo[a]pyrene (BaP), pyrene, atrazine, and 3,3',4,4'-tetrachlorobiphenyl (TCB) as model compounds. Two types of DOM were used, namely Lake Kontiolampi, Joensuu, Finland water (KL) and Nordic reference fulvic acid (NoFA) dissolved in artificial freshwater. Binding of the four contaminants by KL DOM decreased with increasing water hardness. Furthermore, increasing hardness reduced the binding of BaP and pyrene to NoFA. The binding of atrazine and TCB by NoFA was low and was not significantly affected by water hardness. In the DOM-free samples, the bioconcentration of the four contaminants in D. magna usually was not affected by water hardness. In the presence of DOM, the bioconcentration factors (BCFs) were lower (except for atrazine) than in the DOM-free controls. In the presence of both types of DOM, increasing water hardness resulted in higher BCFs for BaP. The bioconcentration of pyrene and TCB increased with increasing water hardness in the presence of KL DOM. In conclusion, the effects of DOM and water hardness on bioavailability of hydrophobic chemicals depend on the type of chemical and on the properties of DOM.

Biological Availability↗