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[Concepts and relative analytical techniques of soil organic matter].

The research of soil organic matter (SOM) has been highlighted in soil science. In the past 50 years, new perspectives in the relationship between SOM and sustainability of atmosphere and biomosphere, and strong motivation to find a vivid index for soil quality variation induced the transformation in concepts and analytical techniques of SOM: the curiousness to humic substances faded off since they were dull to anthropogenic activities, and interests were focused on the light fraction of organic matter (LFOM), organic carbon associated with different mineral particles in size, particulate and intra-particulate organic matter (POM and iPOM), water soluble organic matter (WSOM), and microbial biomass carbon (MB-C). The relative fractionation procedures have been developed, and the main research activities on SOM are transformed from the products of microorganisms (humus) to the organic matter comprised in plant residues at their various decomposition stages and the organic carbon in microorganisms, since they are biologically active and immediately respond to soil cultivation and tillage, crop rotation, and fertilizer application, etc.

Carbon↗

Electron-optical characterization of nano- and micro-particles in raw and treated waters: an overview.

State-of-the-art information is presented on the analysis, by transmission electron microscopy (TEM), of aquatic colloidal particles in the size range of 3 to 500 nm least dimension, with a focus on nanoparticles (1-100 nm). Case studies include selections from both natural waters and waters undergoing treatment. The "species" of nano-particles receiving the greatest attention are: humic substances, polysaccharide fibrils, hydrous iron oxides, viruses, clay minerals, refractory cell debris, and heavy metal agglomerates on biological surfaces. Artifacts and how to both detect and minimize them are outlined. Correlative use of TEM with other imaging techniques is emphasized, along with associated spectroscopy. Noted is the potential of computerized image analysis for quantifying colloids on a "per colloid species" basis, using water samples centrifuged onto electron microscope grids.

Colloids↗

Influence of the size of membrane foulants on the filterability of WWTP-effluent.

The application of membrane filtration for the polishing of wastewater treatment plant (wwtp) effluent is more and more widely used. However, fouling problems are still not well understood. In order to investigate the role of particles in dead-end ultrafiltration of wwtp-effluent, Roorda studied the influence of pre-filtrated wwtp-effluent on the filterability. In addition this research investigates the relation between the filterability of the different fractions in the wwtp-effluent and the amount of organic foulants in these fractions. The results show a relation between the filterability and supra-dissolved particles in the fractions < 0.45 and < 0.2 microm. The amount of COD, colour, proteins and polysaccharides in these fractions are found of minor importance. A significant increase in filterability is found between the fractions < 0.2 and < 0.1 microm as well as a significant decrease in amount of polysaccharides. It is suggested that an essential feature in understanding membrane fouling during ultrafiltration of wwtp-effluent is to investigate the influence of supra-dissolved particles on the filterability as well as the influence of the amount of organic foulants (total organic carbon, proteins, polysaccharides, colour and humic substances) on the reversibility.

Colloids↗

[Research advances in catalytic kinetics of soil oxidoreductase].

Soil oxidoreductase is a group of enzymes catalyzing many important soil biochemical reactions and concerning with the transformation of soil organic matter, formation of humic substance, and dynamics of soil fertility. The catalytic kinetics of oxidoreductase can illuminate its catalytic characteristics, substantial properties, and response to environmental changes. This paper summarized the research advance of its kinetics, and proposed some comments in understanding its action mechanism and in regulating its catalytic processes.

Catalysis↗

Fluorescence characteristic changes of dissolved organic matter during municipal solid waste composting.

Dissolved organic matter(DOM) of municipal solid waste (MSW) consists of minerals, water, ash and humic substances, and is known to enhance plant growth. In this study, inoculating microbes (ZJ, MS) were used in municipal solid wastes composting, and composting implemented a industrialized technology. During composting, dissolved organic matter was extracted from the compost and purified. The spectral characteristics of dissolved organic matter was determined by fluorescence emission, excitation, and synchronous spectroscopy. Fluorescence emission, excitation, and synchronous spectra characterized by different relative fluorescent intensities and peaks over time. Fluorescence spectra were similar to that of fulvic acid in sewage sludge, indicating the presence of dissolved organic matter with aromatic structures and a high degree of molecular polymerization. Compared with the controls with no microbial inoculation, the microbe-inoculated treatments exhibited the increase of aromatic polycondensation, in the following order: MS + ZJ > ZJ > MS > CK.

Bacteria, Aerobic↗

Higher prevalence of goiter in endemic area of blackfoot disease of Taiwan.

Blackfoot disease is an endemic peripheral vascular disorder which is confined to a limited land area on the southwest coast of Taiwan. It has long been related to the consumption of high levels of arsenic found in the artesian well water. Humic substances have also been extracted from the well water and have been reported as a possible source of environmental goitrogen. The purpose of this study was to examine whether the prevalence of goiter is increased in the blackfoot disease-endemic area. This study covered all the children in the elementary schools of Putai and Peimen. They were divided into two groups according to the location of schools in the endemic area or non-endemic area of blackfoot disease. Thyroid enlargement was examined by palpation as recommended by the World Health Organization. Thyroid antibodies and hormones were determined in school children with a goiter and age-sex-matched normal control children using particle agglutination methods and radioimmunoassays, respectively. Aspiration cytology was done in cases with a nodular goiter. In total 4,567 school children were examined, including 2,306 males and 2,261 females. One hundred and twenty school children (2.63%) had a goiter of grade I or above. The prevalence of goiters in school children from the endemic area was higher than that from the non-endemic area (3.44 vs 2.08%, p less than 0.01). The prevalence of goiters in females from the endemic area was higher than that from the non-endemic area (4.65 vs 2.69%, p less than 0.02).(ABSTRACT TRUNCATED AT 250 WORDS)

Biomarkers↗

[The role of goitrogenic factors distinct from iodine deficiency in the etiology of goiter].

The main cause of endemic and sporadic goiter is a deficiency in the dietary supply of iodine. However, iodine deficiency is not the only cause of goiter. This paper reviews present knowledge on the role of naturally occurring goitrogens in the etiology of goiter. Vegetables from the Cruciferae family, chronic consumption of poorly detoxified cassava containing large amounts of cyanogenic glucosides, flavonoids, humic substances originating from the organic residues in the soil are clearly involved in the etiology of endemic goiter. Iodine excess, especially in the newborn infants, lithium and thiocyanate overload resulting from smoking habits can be responsible for the development of goiter in non endemic areas.

Goiter↗

[Nature of the stimulating action of parenterally administered casein hydrolysate on gastric secretory function].

Experiments on 4 gastric fistula dogs kept on full-value diet were made in an effort to specify the character of the stimulatory action of parenteral caseine hydrolysate (TSOLIPK) on the gastric fundal glands. In the course of administering the solutions similar to individual components of casein hydrolysate into the blood it was established that the secretory effect of the protein hydrolysate is not a consequence of the presence of ammonia contained by the hydrolysate or depends on the humic substances. It is assumed that the stimulatory action of parenteral casein hydrolysate on the gastric fundal glands is determined by the main protein break down products, i.e. by amino acids and peptides that are capable of acting on the nerve structures and of stimulating gastric secretion via excitation of the centres responsible for gastric function control.

Amino Acids↗

[Risk for the Rostock water supply from the Warnov river by an old deposit at Schwann?].

Accidents of the city gasworks in the end of the fifties at Schwaan, a small town south of Rostock, resulted in an emission of tar and waste water into the river Warnow, from which the city of Rostock is supplied with drinking water about 20 km downstream. The tar contaminated river sediment (old deposit) covering an area of about 200 m2 has a high pollutant inventory: Steam-distillable phenolic compounds 407 mg/kg in the fresh sediment, polycyclic aromatic hydrocarbons (PAH) 400 to 1100 micrograms/l in the aqueous eluate. The mutagenic potential was detected by the AMES-test. As shown by PAH determinations there were no other pollutant sources in the catchment area, in the tributaries or on other places of the river. The mean PAH concentrations of the river Warnow and his tributaries during 1991 to 1994 were found to be in the range lower than 10 ng/l. Further investigations showed a continuous emission of PAH from the tar laugh in small amounts. An additional emission of pollutants (PAH) and their transportation in the river is expected in the case of sediment disturbances. This emission and their possible consequences are difficult to estimate, even though the seston and the humic substances content of the river seems to reduce the PAH risk. Concluding from our results the probability is very low that pollutants were transported downstream to Rostock and pass the water works but may not totally be excluded. Nevertheless from the viewpoint of care a removal of the old deposit is necessary.

Fresh Water↗

Selenium and arsenic in the environment in Finland.

A characteristic feature of glaciated Precambrian environments is their low selenium content, as a chalcophile element, Se, replaces sulfur in many of the sulfide minerals, for example, pyrite, chalcopyrite, pyrrhotite, and pentlandite. The average Se concentration in rocks and related till deposits in Finland is in the range of 0.01 to 0.2 mg/kg. Due to geological conditions, Se concentrations in surface and ground water are low in Finland compared with other countries. In a nationwide study dealing with the hydrogeochemistry of headwater streams, the median Se concentration in streams during August to September 1990 was 30 to 180 microg/L. For comparison, Se concentrations in shallow well waters are generally in the range of 50 to 1000 microg/L. The Se concentrations in stream sediments varied from 0.03 to 3.94 mg/kg. There was a highly significant correlation between the Se concentrations in stream water and in stream sediment. The streams with Se concentrations exceeding the general level in both water and sediment were most common in southern Finland. A speciation study on Finnish stream waters revealed that there were equal proportions of Se complexed with humic substances (36%) and Se as a selenate species (36%), whereas selenite accounted for less than 10% of total Se. About 8% of the Se in stream water occurred in particulate form. In an effort to enhance the Se intake of Finns through diet, Se-supplemented fertilizers have been used nationwide since 1985. While greatly improving Se levels in the population, the measure has raised concerns about undesirable environmental effects. Therefore, the amount of Se added to fertilizers has been reduced since 1991. Differing in behavior from Se, arsenic is considered one of the most toxic metals derived from the natural environment. Alarm has been triggered in Finland by the recent lowering from 50 microg/L to 10 microg/L of the upper level of As permissible in potable water, the recent information of high As concentrations in water from drilled bedrock wells, and the findings of international medical studies suggesting that As is a carcinogen. The most important source of As is arsenopyrite (FeAsS). Hence, high As concentrations most frequently occur in areas of sulfide mineralization, often in connection with occurrences of mafic rocks such as gabbros, amphibolites, and peridotites. The As concentrations in till fines, the most common glaciogenic soil type in Finland, reflect those in bedrock. The concentrations in groundwater are controlled by the chemical composition of the bedrock and the soil and prevailing hydrogeochemical conditions, for example, pH and Eh levels. Arsenic concentrations are lowest in surface water and swiftly flowing shallow ground water discharged by springs and are somewhat higher in shallow wells dug into overburden. By far, the highest As concentrations are to be found in wells drilled into bedrock (maximum 1 to 2 mg/L), although the concentrations vary by several orders of magnitude from well to well. The highest probability of encountering deleteriously arsenious well water is in areas with characteristic As anomalies in the till and bedrock. Hence, it is important to understand local geological conditions, particularly in the case of wells drilled into bedrock. The risk of deleteriously high As concentrations occurring in captured springs and shallow wells is slight.

Animals↗

[Pharmacologic and toxicologic properties of humic acids and their activity profile for veterinary medicine therapy].

Humic acids derive from a class of natural substances in humic substances. The chemical properties of certain defined humic acid products enable their application in diseases of the digestive system of mammals when combined with metabolic disorders, especially in rearing age. The simple administration (via feed), their exceptional safety and the absence of side effects (e. g. allergy, resistance) as well as no residue formation in animal derived products allow a broad application of these substances in veterinary medicine, even when regarding ecotoxicological aspects.

Animals↗

Characterization of extracellular polymeric substances in rotating biological contractors and activated sludge flocs.

Extracellular polymeric substances (EPS) from biofilms of a rotating biological contactor (RBC) system and from activated sludge flocs were extracted using ultrasound and a cation exchange resin. In both wastewater treatment systems, the EPS matrix was mainly constituted of proteins, humic-like substances and polysaccharides, although other components--DNA and uronic-like substances--were also present. The composition of the biofilm EPS was different in the succesive RBC wastewater treatment stages: protein had its highest concentration in the first RBC unit, while humic substances and polysaccharides in the third RBC. Significant differences between biofilm and sludge floc EPS were also reported. The amount of proteins was 3.5 times higher for RBC biofilms than for sludge flocs, and quantities of humic substances and polysaccharides extracted from biofilms were twice as high than in sludges. Moreover, biofilm exopolymers were two times more hydrophobic than those of sludge flocs. Implications of wastewater chemistry and microbial growth strategies into EPS composition and properties are suggested.

Biofilms↗

Selective electrochemical detection of ionic and neutral species using films of Suwannee River humic acid.

An electroanalytical method has been developed to investigate the uptake of redox-active species by the humic acid substances. The Suwannee River humic acid (SHA) films were first cast on a glassy carbon electrode using an electrophoretic approach. The binding of a series of redox-active species to these SHA films was then probed using cyclic voltammetry at a rotating disk electrode. Neutral molecules such as hydroquinone and cationic species such as methyl viologen are able to bind with the humic membrane and exhibit high redox activity within the film. On the other hand, anionic species such as ferrocyanide are unable to attach themselves to the SHA films and thus exhibit negligible electrochemical activity. Cyclic voltammetric study of SHA films has also facilitated the determination of the partitioning constants and identification of the effect of coadsorbed ions (Ca2+) on the binding of redox species. The electroanalytical method described in this study opens up new avenues to examine the interactions and transport of charged species in a humic acid environment.

Electrochemistry↗

XAFS studies of cobalt(II) binding by solid peat and soil-derived humic acids and plant-derived humic acid-like substances.

This work has examined cobalt(II) binding by a variety of solid humic acids (HAs) isolated from peat, plant and soil sources at temperatures down to 60K. The results confirm that X-ray absorption near-edge spectroscopy (XANES) measurements cannot distinguish between aquo and carboxylato ligands in the inner coordination sphere of Co(II). However, between 1 and 2 inner-sphere carboxylato ligands can be detected in all the peat, plant and soil-derived HA samples by extended X-ray absorption fine structure (EXAFS) measurements, indicating inner-sphere coordination of HA-bound Co(II). The precision of C(carboxylate) detection is limited by the extent and quality of the data and the contribution from inner-sphere O to the Fourier transformed peaks used to detect carbon. Putative chelate ring formation is consistent with a relatively negative entropy change in step A, the stronger Co(II) binding step by HA functional groups, and could relate to 'non-exchangeable' metal binding by HSs.

Cobalt↗

Evaluation of refractory organic removal in combined biological powdered activated carbon--microfiltration for advanced wastewater treatment.

Biological powdered activated carbon (BPAC) was incorporated with a microfiltration (MF, 0.2 micron pore size) system to remove the refractory organic matter contained in secondary sewage effluent. A synthetic secondary sewage effluent was used as influent in this study, containing both non-biodegradable organic substances (such as humic acid, lignin sulfonate, tannic acid and arabic gum powder) and biodegradable ones. These refractory organic materials were possibly degraded in contact with microorganisms for 20-27 days. Although humic acid and arabic gum were weakly adsorbed on the activated carbon, they could be effectively removed in the BPAC reactor. The TOC removal at a powdered activated carbon (PAC) concentration of 20 g/L was higher than at 0.5-2 g PAC/L (83% and 66-68%, respectively). The higher removal efficiency was due to the increased rejection at the membrane module in which most of the PAC was accumulated. More than 90% of non-biodegradable compounds removal (detected as E280, UV absorption at 280 nm) occurred in the BPAC reactor. The biological growth parameter b/Y, used in system design, was estimated to be 0.017 d-1. Relatively high permeate flux of 1.88 m/d could be obtained even at higher PAC concentration of 20 g/L.

Adsorption↗

A modified procedure for the determination of nitrate in sediments and some natural waters.

This paper describes a modified procedure for the determination of nitrate in sediments and some natural water samples. In the Water Quality Branch Laboratories where large numbers of samples are regularly analysed, it was found that existing methods1,4 do not give precise and accurate results particularly when applied to sediment samples and some natural waters. The reasons for such inaccuracies have sebsequently been found and a method for removal of such interfering substances have been devised. The proposed method essentially consist of two steps. In the first step the interfering substances such as sulfide and humic acid substances are removed by precipitation with copper. The resultant solution is then analysed by a colorimetric approach utilizing cadmium fillings as the reducing agent to reduce nitrate to nitrite, and analyse the resultant nitrite with sulfanilamide, and naphtylene diamine. The smallest amount of nitrate that can be detected with certainty is approximately 10 mug-at N/Kg and 50 mug/ at N/Kg in water and sediments respectively. The figures for sediments are based on dissolving 20 gms. of sediment, dry weight, in 100 ml volume. The proposed method has been tested on a wide variety of natural water samples, sediments, clays and sands.

Chemical Precipitation↗

Composition of a protein-like fluorophore of dissolved organic matter in coastal wetland and estuarine ecosystems.

This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation-emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r(2)=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5 x 10(4) (T(1)) and approximately 7.6 x 10(3) (T(2)) and with varying relative abundance among samples. The T(1)-peak intensity correlated strongly with [UDON] (r(2)=0.516, p<0.001), while T(2)-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.

Chromatography, Gel↗