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PubMed2004

The impact of rainstorm events on coagulation and clarifier performance in potable water treatment.

This paper examines turbidity removal at a water treatment works in England that receives raw water which is difficult to treat during certain rainstorm events. Rainstorm events lead to elevated levels of turbidity and organic matter found in river waters. A robustness index based on settled turbidity was used to identify periods and events that adversely affected the treatment process. This coupled with raw water sampling data indicated that a change in nature and an increase in natural organic matter (NOM) concentrations occurred following rainstorm events. Experimental work investigated the effect of temperature and NOM on the coagulation process and the results show how increasing levels of NOM significantly impaired the coagulation of particulate material, leading to an increase in settled turbidity.

England↗

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

Copper complexing properties of melanoidins and marine humic material.

Melanoidins, condensation products of sugars and amino acids, represent a key link in the transformation of polysaccharides to humic material in the marine environment. We investigated the complexing capacity of melanoidins that were prepared in deionized water and seawater and separated into different molecular mass fractions. The copper complexing properties of humic material isolated from marine lagoon sediments were determined for comparison. Melanoidins prepared using condensation times longer than two days exibit complexation properties towards copper ions that appear to depend on the basicity of the amino acid precursor and the molecular mass of the product. Pseudomelanoidins, prepared from glucose only, do not complex copper ions at all, regardless of the molecular mass. The highest copper complexing capacity value among melanoidins was measured for a glucose-lysine melanoidin with molecular mass fraction >10 kD (L(T)=2.1x10(-7) molCu(2+)/L). Melanoidin prepared from glucose and glutamic acid >10 kD was similar in complexing capacity to fulvic acid (1-20 kD molecular mass) isolated from lagoon sediments. The presence of calcium and magnesium ions and other macro and microconstituents in the seawater used to prepare melanoidins influences its complexing properties towards metal ions.

Amino Acids↗

PubMed2005

Spectroscopic evidence of the marine origin of mucilages in the Northern Adriatic Sea.

Vibrational Fourier transform infrared (FTIR) and UV-Visible spectroscopies coupled to thermogravimetry were used to characterise the gelatinous aggregates as well as the humin and humic fractions extracted from the aggregates. Spectroscopic analysis made it possible to identify the main classes of compounds present in the samples. The FTIR spectra of the aggregates showed the presence of carbohydrates, saturated aliphatic compounds, aminic, esteric, amidic (proteins) and ketonic compounds, organic and inorganic phosphates, silica and, in some cases, carbonates. The FTIR spectra of humin and humic acids showed functional groups similar to those found in the spectra of the aggregates. The high aliphatic character and the absence of aromatic compounds observed in many aggregates sampled far from estuarine areas suggest the marine origin of mucilages. These results were also confirmed by the 270/407 nm (A2/A4) and 465/665 nm (E4/E6) absorbance ratio in humic acids.

Algal Proteins↗

PubMed2006

Characterizing natural organic material from the Occoquan Watershed (Northern Virginia, US) using fluorescence spectroscopy and PARAFAC.

Surface water samples from the Occoquan Watershed (Virginia, US) were collected during summer baseflow conditions and characterized by excitation-emission matrix (EEM) fluorescence spectroscopy and parallel factor analysis (PARAFAC). Based on 55 samples, PARAFAC identified three individual fluorophore moieties, which were attributed to humic-like, fulvic-like, and protein-like materials. The categorization of these seemingly universal fluorophore moieties in aqueous systems was consistent with expected analyte concentrations that were independently measured by traditional wet chemistry techniques. The relative distribution of the three fluorophore fractions varied among the different land use catchments, especially in locations of known anthropogenic activity. Distinctive relationships between the fulvic-like and protein-like materials were observed for catchments known to be influenced by anthropogenic activity and those believed to reflect more natural environments, suggesting that this technique could be used to monitor human impact on aquatic systems. Finally, PARAFAC can be used to provide estimates (+/-30%) of select analyte concentrations in surface water. The results of this study support the use of EEM and PARAFAC analyses by watershed managers and other personnel interested in understanding organic matter behavior in aquatic systems.

Benzopyrans↗

PubMed2006

Photodegradation of endocrine disrupting chemical nonylphenol by simulated solar UV-irradiation.

The photolysis of nonylphenol (NP) was investigated using a solar simulator in the absence/presence of dissolved organic matter (DOM), HCO3-, NO3- and Fe(III) ions. The effects of different parameters such as initial pH, initial concentration of substrate, temperature, and the effect of hydrogen peroxide concentration on photodegradation of nonylphenol in aqueous solution have been assessed. The results indicate that the oxidation rate increases in the presence of H2O2, Fe(III) and DOM with dissolved organic carbon concentrations not higher than 3 mg L(-1). Phenol, 1,4-dihydroxylbenzene and 1,4-benzoquinone were identified as intermediate products of photodegradation of nonylphenol, through an HPLC method. In addition, the disappearance of the estrogenic activity of nonylphenol during irradiation using YES test was investigated. Based upon the YES test results, there was a strong decrease of estrogenic activity of nonylphenol after 80 h irradiation in the presence of hydrogen peroxide.

Bicarbonates↗

PubMed2007

Mobilization and speciation of chromium in compost: a methodological approach.

An integral approach to study the mobility of chromium in compost is presented. The approach is based on batch pH dependence leaching tests and the analysis of the leachates for total chromium, chromium(VI) and complexes of chromium(III) with natural organic matter. As leachings are performed with no aggressive reagents (ultrapure water with added nitric acid or potassium hydroxide), the method can be considered a good approach to simulate natural scenarios. The analysis of leachates is complemented with the determination of total chromium and total Cr(VI) in the solid sample. Speciation analysis are done by high performance liquid chromatography with inductively coupled plasma mass spectrometry as detection technique; Cr(VI) is determined by ion chromatography, whereas Cr(III) complexes with natural organic matter by size exclusion chromatography. In the compost studied, Cr(VI) accounted for 6% of the total chromium in the solid, whereas no significant amounts of Cr(VI) were mobilized in the pH range studied (4-10). Chromium is mobilized as Cr(III) bound to organic matter, both to humic and fulvic acids, with an increasing contribution of humic acids at higher pHs.

Benzopyrans↗

PubMed2004

Separation of aromatic-carbon 13C NMR signals from di-oxygenated alkyl bands by a chemical-shift-anisotropy filter.

Selection of alkyl-carbon and suppression of aromatic-carbon 13C nuclear magnetic resonance (NMR) signals has been achieved by exploiting the symmetry-based, systematic difference in their 13C chemical-shift anisotropies (CSAs). Simple three- or five-pulse CSA-recoupling sequences with "gamma-integral" cleanly suppress the signals of all sp2- and sp-hybridized carbons. The chemical-shift-anisotropy-based dephasing is particularly useful for distinguishing the signals of di-oxygenated alkyl (O-C-O) carbons, found for instance as anomeric carbons in carbohydrates, from bands of aromatic carbons with similar 13C isotropic chemical shifts. The alkyl signals are detected with an efficiency of > 60%, with little differential dephasing. Combined with C-H dipolar dephasing, the CSA filter can identify ketal (unprotonated O-C-O) carbons unambiguously for the first time. Conversely, after short cross polarization and the CSA filter, O-CH-O (acetal) carbon signals are observed selectively. The methods are demonstrated on various model compounds and applied to a humic acid.

Algorithms↗

PubMed2006

A molecular dawn for biogeochemistry.

Biogeochemistry is at the dawn of an era in which molecular advances enable the discovery of novel microorganisms having unforeseen metabolic capabilities, revealing new insight into the underlying processes regulating elemental cycles at local to global scales. Traditionally, biogeochemical inquiry began by studying a process of interest, and then focusing downward to uncover the microorganisms and metabolic pathways mediating that process. With the ability to sequence functional genes from the environment, molecular approaches now enable the flow of inquiry in the opposite direction. Here, we argue that a focus on functional genes, the microorganisms in which they reside, and the interaction of those organisms with the broader microbial community could transform our understanding of many globally important biogeochemical processes.

Biochemistry↗

PubMed2005

Angiogenesis and cardioprotection after TNFalpha-inducer-Tolpa Peat Preparation treatment in rat's hearts after experimental myocardial infarction in vivo.

The aim of the presented work was to evaluate whether short subcutaneous (s.c.) administration of TNFalpha-inducer-Tolpa Peat Preparation (TPP or TPP batch 0210) modulates the process of ischemic remodeling and spontaneous angiogenesis after experimental myocardial infarction (MI) in rats in vivo. The results obtained using three complementary and correlative methods: histological studies, Proliferating Cell Nuclear Antigen (PCNA) reaction and Lymphocytes Induced Angiogenesis (LIA) test showed a clear pro-angiogenic and cardioprotective effect of TPP administration after experimental MI. TPP batch 0210 should be considered as an angiogenesis stimulating factor and consecutively as a cardioprotective preventing development of ischemic cardiomyopathy after MI in rats. It might possibly be used as an adjunct to conventional therapy of coronary artery disease, including late phase after myocardial infarction or ischemic cardiomyopathy.

Amino Acids↗

PubMed2005

Changes in organic matter composition during composting of two digested sewage sludges.

Changes in the chemical and chemical-structural composition of the organic matter of two different sewage sludges (aerobic and anaerobic) mixed with sawdust (1:1 and 1:3, v/v) during composting were determined by monitoring chemical and microbiological parameters as well as by pyrolysis-gas chromatography. Composting was carried out in periodically turned outdoor piles, which were sampled for analysis 1, 30, 60 and 90 days after the beginning of the composting process. Both volatile organic matter and the water soluble C fraction decreased during composting, indicating that the more labile C fractions are mineralized during the process. Microbial activity as measured by microbial respiration (CO(2) evolved from compost samples during incubation) also decreased with composting, reflecting the more stable character of the resulting compost. No major differences were observed between the four composts studied as regards their chemical-structural characteristics. The acetonitrile, acetic acid and phenol pyrolytic fragment tended to increase with composting. Although the final composts were more aromatic in nature than the starting materials, a low degree of humification was observed in all four composts studied, as determined by their high proportion of polysaccharides and alkyl compounds. For this reason, the relationship between pyrolytic fragments, such as benzene/toluene or benzene+toluene/pyrrol+phenols, which are used as indices of humification for soil organic matter, are not of use for such poorly evolved sludge composts; instead, ratios that involve carbohydrate derivatives and aromatic compounds, such as furfural+acetic/benzene+toluene or acetic/toluene, are more sensitive indices for reflecting the transformations of these materials during composting. Both the chemical and microbiological parameters and pyrolytic analysis provided valuable information concerning the nature of the compost's organic matter and its changes during the composting process.

Aerobiosis↗

PubMed2006

Modification of soil humic matter after 4 years of compost application.

Two soil plots, 1 ha each, were amended yearly for 4 years, respectively, with 35.8 and 71.6 Mg ha(-1) yr(-1) of mature compost (CM) obtained from food and vegetable residues. The compost, amended soils, and a control soil plot after 4 years (S4), were analyzed for humin (HUC), humic acid (HAC), fulvic acid (FAC), and non-humic carbon (NHC) content. Compared to S4, the amended soil contained more humified C (HAC, FAC and HUC) and less NHC. Further evidence of the effect of compost on soil organic matter was obtained by the analysis of the humic acid (HA) fractions isolated from both the compost and the soils. These were characterized by elemental analyses and Diffuse Reflectance Infrared Fourier Transformed spectroscopy. The HAs isolated from CM and from S4 were significantly different. The HAs isolated from the amended plots were more similar to HA isolated from CM than to HA isolated from S4. The experimental data of this work indicate that the compost application may affect significantly the soil organic matter composition, and that the approach used in this work allows one to trace the fate of compost organic matter in soil.

Biodegradation, Environmental↗

PubMed2006

A multivariate approach to the study of the composting process by means of analytical electrofocusing.

Three blends formed by: agro-industrial waste, wastewater sewage sludge, and their mixture, blended with tree pruning as bulking agent, were composted over a 3-month period. During the composting process the blends were monitored for the main physical and chemical characteristics. Electrofocusing (EF) was carried out on the extracted organic matter. The EF profiles were analyzed by principal component analysis (PCA) in order to assess the suitability of EF to evaluate the stabilisation level during the composting process. Throughout the process, the blends showed a general shifting of focused bands, from low to high pH, even though the compost origin affected the EF profiles. If the EF profile is analyzed by dividing it into pH regions, the interpretation of the results can be affected by the origin of compost. A good clustering of compost samples depending on the process time was obtained by analyzing the whole profile by PCA. Analysis of EF results with PCA represents a useful analytical technique to study the evolution and the stabilisation of composted organic matter.

Animals↗

PubMed2004

Integrated biofilter-immersed membrane system for the treatment of humic waters.

An integrated biofilter-immersed membrane study was conducted to determine the effect of placing a biofilter before or after a membrane for the treatment of a humic type water. The parameters measured included total organic carbon (TOC), organic acids, and specific ultraviolet absorbance (SUVA). The difference in membrane fouling and microbial growth for the two configurations was also examined. Greater TOC and organic acid removal occurred when the biofilter was located ahead of the membrane. The greatest decrease in SUVA values was associated with the membrane. The membrane located after the biofilter fouled at a slower rate than the membrane ahead of the biofilter. Fouling was slower when turbidity was present in the synthetic feedwater. A new method is proposed for determining the operational cleaning frequency of membranes, using an empirical model.

Bacteria↗

PubMed2004

Combination of ferric and MIEX for the treatment of a humic rich water.

Seasonal periods of high rainfall have been shown to cause elevated natural organic matter (NOM) loadings at treatment works. These high levels lead to difficulties in removing sufficient NOM to meet trihalomethane (THM) standards, and hence better alternative treatments are required. Here the removal of NOM was investigated by a new ion exchange process (MIEX) using both bulk and fractionated NOM. Initial results showed that in excess of 80% of the raw water dissolved organic carbon (DOC) and greater than 85% of the UV absorbance from the bulk raw water could be removed by the use of MIEX alone. It was also seen that the removal of the more recalcitrant isolated fractions was increased. When MIEX was combined with a significantly reduced dose of coagulant a slight improvement on the overall DOC and UV removals was observed, however a significant decrease in the amount of THM formation potential (THMFP) in the final water was seen. This combined with the reduction in coagulant would imply a more efficient process during the times when the water becomes increasingly difficult to treat.

Carbon↗

PubMed2004

Effect of phenolic mediators and humic acid on cyprodinil transformation in presence of birnessite.

Naturally occurring phenols were evaluated as mediators for the transformation of the fungicide cyprodinil by birnessite. With birnessite alone, cyprodinil transformation was negligible (0.6%). In the presence of mediators, however, it increased considerably (1.5-60.9%). With some exceptions (2,6-dimethoxyphenol, syringic acid), methoxylated phenols showed a substantial capacity for enhancing the transformation. Mass spectrometry indicated that cyprodinil cross-coupled with free radicals of phenols formed at birnessite surfaces. The extent of cyprodinil transformation in the presence of syringaldehyde, m-methoxyphenol, or vanillin increased with the amount of birnessite. In reactions with o- and p-methoxyphenol and vanillic acid, cyprodinil transformation was unaffected by the amount of birnessite, but it increased with increasing phenol concentration. The addition of various humic acids at low concentrations (5-10 mg/L) had little effect on cyprodinil transformation in the presence of o-methoxyphenol or syringaldehyde. At higher concentrations, however, humic acids inhibited the transformation (by 5-20%) when o-methoxyphenol was a mediator, but showed no effect in the presence of syringaldehyde.

Biotransformation↗

PubMed2004

Comparative study of humic acids flocculation with chitosan hydrochloride and chitosan glutamate.

Flocculation of dissolved humic acids (HA) and their complexes with metal ions and organic pollutants is a crucial step in drinking water preparation due to significant undesirable effects of humic compounds on water quality. Constant demand for cheap, effective and environmentally friendly flocculants brings about the interest to natural cationic polymers which can be used to neutralize negative charge of humic colloids through polyelectrolyte complexes (PEC) formation. In this work, the interaction of HA with two types of soluble chitosan salts (hydrochloride and glutamate) at different pH and polymer ratios was studied with a focus on electrical charge of PEC formed and effectiveness of color removal in the flocculation process. For both chitosan forms flocculation window was found at pH close to the PEC isoelectric point (pI) in a wide concentration range; however, lower flocculant dose was required when chitosan glutamate was used.

Biocompatible Materials↗

PubMed2004

Removal of fulvic acid from water electrochemically using active carbon fiber electrode.

Humic acids (HA) are a group of widely existing natural organic compounds and potential contaminants to underground water reservoirs. Fulvic acid (FA) is a typical humic acid of relatively low molecular weight. Electrochemical removal of FA from water by active carbon fiber (ACF) electrodes was studied by using light scattering photometer (LSP), fluorescence spectroscopy and total organic carbon analyzer (TOC). The experiments showed that FA molecules aggregated and that the average particle diameter in FA solution increased from below 10 nm to hundreds of nanometers during the treatment process. When iron was added to the anode, the FA could be coagulated efficiently at the early stage of the treatment. The proposed mechanism of the removal process is: adsorption of FA on ACF surface --> aggregation of FA --> desorption of FA aggregates from ACF --> coagulation of FA aggregates by nFe(OH)(2).mFe(OH)(3) dissolved from anode. Experiments were also repeated using graphite and stainless-steel electrodes, and the results were compared with that of ACF electrodes. FA aggregation was not observed in these experiments and most FA was not removed from the solution. At the end of this paper, FA samples from Huai River sediment were successfully treated using the ACF electrode.

Adsorption↗