Fulvic acid in microlayer waters of the Gerlache Inlet Sea (Antarctica): their distribution in dissolved and particulate phases.

In this work we studied the distribution of humic compounds between microlayer and subsurface waters. Both dissolved (DFA) and particulate (PFA) matter were considered. Humic acids were not found. The amount of total particulate matter is the same both in microlayer and subsurface waters. Conversely, particulate organic matter and fulvic acid concentrations were greater in microlayer waters. Enrichment factors (microlayer PFA/subsurface PFA and microlayer DFA/subsurface DFA) show a greater presence of fulvic acids in the microlayer. Moreover, the enrichment process is greater for the particulate phase. C/N values both in microlayer and subsurface waters are greater for DFA with respect to PFA and C/N values for DFA of microlayer are greater than that of subsurface waters. So DFA could be older than PFA, and DFA of subsurface waters younger than that of microlayer waters. For PFA S/C ratios in microlayer waters are greater than that of subsurface waters, underlining that the enrichment process is selective as regards sulphur-containing structures.

Reduction of Pb and Zn bioavailable forms in metal polluted soils due to paper mill sludge addition. Effects on Pb and Zn transferability to barley.

In the last few years solidification/stabilisation of acidic soils polluted by heavy metals with low-cost sorbents has been investigated. Paper mill sludges are produced in large amounts and their disposal is a serious environmental problem. The possibility was therefore studied of using paper mill sludge as a stabilizer to reduce the bioavailable metal forms in polluted soils and thus the transferability of metals to plants (barley). We first investigated the sorbing properties of paper mill sludge for Zn(II) and Pb(II) and then their fractionation both in a polluted soil and in the same soil amended with paper mill sludge in order to check the decrease in mobile forms. Finally in both soils we tested the uptake of two metals by common barley in order to assess the performance of soil remediation from an ecological point of view. The addition of paper mill sludge to a soil contaminated by lead and zinc induces a decrease in the mobile forms of both metals, probably due to the presence in sludge of organic matter and kaolinite, which are able to bind the metals very strongly. The decrease in the mobile forms, which are the most readily available for uptake by plants, corresponds to a decrease in plant uptake.

Complexation of cadmium and copper by fluvial humic matter and effects on their toxicity.

The effects of humic acids and fulvic acids isolated from the River Arno (Italy) on the bioavailability and toxicity of cadmium and copper were assessed in relation to changes in their speciation. Measurements of the complexing capacity of solutions containing these organic ligands were carried out by a titration procedure followed by DPASV and toxicity tests were carried out using lysosomes isolated from rat liver. The complexing capacity of the physiological medium containing about 13 mg/L of humic acids, expressed as ligand concentrations, was 0.30 and 0.072 micromol/L for cadmium and copper respectively; the corresponding conditional stability constants were 4.2 x 10(11) and 1.3 x 10(8) (mol/L)-1. The complexing capacities of the solution containing the same amount of fulvic acids were 0.33 and 0.164 micromol/L for cadmium and copper respectively, the conditional stability constants were 3.2 x 10(11) and 2.4 x 10(7) (mol/L)-1. The humic acids reduced the toxicity of cadmium by about 5 times: the EC50 changed from 4.4 to 20.4 micromol/L. The dose effect curve of copper presented a bi-sigmoid trend and two EC50 values can be determined: The EC50(1) in the presence of humic acids changed from 2.0 to 3.1 micromol/L, while the EC50(2) increased from 22.3 to 45.3 micromol/L. The fulvic acids reduced the cadmium toxicity by about the same amount as humic acids, from 4.4 to 18.6 micromol/L, but they had no effect on copper toxicity. Analysing the chemical speciation of cadmium and copper in the presence of humic components and under toxicity test conditions we can say that the appreciable decrease of EC50 is not related to changes in their speciation; we can hypothesize that this is due to different processes, as well as to blocking of the lysosomal membrane. On the basis of the shape of the dose-effect curves obtained for cadmium and copper respectively, we can say that the toxic effects of the two metals are different and we can hypothesize that copper could exercise its toxic activity by inhibiting the ATP-driven proton pump and the function of the Cl- selective channel.

Dissolved and particulate humic substances in water channels in the historic centre of Venice.

The presence of humic substances, both in solution and as particulate, was studied in channels of the historic centre of Venice. The amount of particulate, its composition (organic and inorganic fraction) and the ratio between organic matter and humic substances were also considered. The sampling campaign was planned in 2001-02 from November to May. Three samplings in 20 stations representative of a large typical urban area were performed. The results obtained show that the composition of the particulate is variable, whereas the concentration of both dissolved and particulate humic substances is relatively homogeneous. Fulvic acids present in particulate are less homogeneous than dissolved forms; furthermore, the humification rate of organic matter is variable. Humic acids are absent, both in particulate and in dissolved forms.

Sedimentary humic substances in the northern Adriatic sea (Mediterranean sea).

Humic compounds were determined in sediments collected in an area of the Adriatic sea receiving fresh waters from the river Po. Sediment cores (10 cm) were sectioned into four layers which were analysed separately for redox potential (Eh), total phosphorus (TP), total organic carbon (TOC), humic (HA) and fulvic acid (FA) content. The structure of HA and FA was also investigated. The results showed that the TOC and TP content decreased from the coast to the open-sea stations. Humic and fulvic acid concentrations were also inversely correlated to the distance from the coast. Moreover, the humic and fulvic acids were closely correlated to the total organic content and to the total phosphorus content. The correlations found between humic substances (HS) and TOC and TP, respectively, could be explained both by an in situ formation due to the high content of nutrients and organic matter, and by a common source of HS, TOC and TP, namely the River Po discharge. The predominant presence of aliphatic carbon in the humic structures, the low degree of substitution and the high nitrogen content suggest that primarily humified compounds were formed in situ. Nevertheless, the River Po can act both as supplier of organic matter of which decomposition products lead to the formation of humic compound and as carrier of humified compounds.

Metal-contaminated soil remediation by means of paper mill sludges addition: chemical and ecotoxicological evaluation.

Metal pollution of soils is a great environmental problem. The major risks due to metal pollution of soil consist of leaching to groundwater and potential toxicity to plants and/or animals. The objective of this study is to evaluate by means of chemical and ecotoxicological approach the effects of paper mill sludge addition on the mobile metal fraction of polluted metal soils. The study was carried out on acidic soil derived from mining activities and thus polluted with heavy metals, and on two paper mill sludges having different chemical features. The results obtained by leaching experiments showed that the addition of a paper mill sludge, consisting mainly of carbonates, silicates and organic matter, to a heavy-metal polluted soil produces a decrease of available metal forms. The carbonate content seems to play a key role in the chemical stabilisation of metals and consequently in a decrease of toxicity of soil. The leached solutions have a non-toxic effect. The mild remediation by addition of sludge has moreover a lasting effect.

Some applications of ligand-exchange-II Separation of phenolic compounds.

The separation of phenol, 2-nitrophenol, 2,4-dichlorophenol and pentachlorophenol by ligand-exchange chromatography was studied with Chelex 100 resin in the Fe(3+) form as stationary phase and sodium hydroxide solution (pH 7.5, 11.5, 12) as the mobile phase.

Some applications of ligand-exchange--I. Recovery of phenolic compounds from water.

The properties of a chelating ion-exchanger in the iron(III) form in contact with an aqueous solution containing phenolic compounds have been studied. The phenols retained are completely displaced by elution with an ethanolic sodium hydroxide solution.

Determination of tin and triorganotin compounds in sea-water by graphite-furnace atomic-absorption spectrophotometry.

An analytical method based on graphite-furnace atomic-absorption spectrophotometry employing a suitable signal-enhancing medium for determination of inorganic tin and two of its trisubstituted organic derivatives in sea-water has been established. This method allows determination of triphenyltin and tributyltin compounds down to 2 x 10(-12) and 2.8 x 10(-12)M respectively by means of enrichment by collection on graphitized carbon black (enrichment factor up to 8 x 10(4)) and a separation on a small silica-gel column. Inorganic tin, which is not adsorbed on the graphitized carbon black, is isolated from the matrix by liquid-liquid extraction of its pyrrolidinedithiocarbamate complex into dichloromethane. The method gives good recovery (95%) and precision ( less, similar5%) at the ng/l. level.

Applications of ligand-exchange-III Preparation and properties of phenol-formaldehyde-based resin in the iron(III) form.

A number of resins containing ethylenediamine acetic acid groups have been prepared, and these intermediates (resin-EDTA) converted into the iron(III) form. The capacities of these exchangers in the formation of iron(III)-phenol complexes have been studied and compared with those of the Chelex-iron(III) resin. The character of the exchanger matrix is very important in connection with the retention of phenols and with the elution order. The modified Amberlite CG 4B in the iron(III) form can be used for the quantitative separation of phenolic compounds, a separation that is not possible with the Chelex-iron(III) resin.

Determination of organophosphorus pesticides by thin-layer chromatography.

Analysis for 13 common organophosphorus pesticides by thin-layer chromatography is described; 17 solvent systems were examined. With channel thin-layer chromatography, linear calibration graphs were obtained for the range 1-10 mug.

Purification of soluble fulvic acid low concentrations by a diafiltration technique.

The purification of soluble fulvic acids (FA) based on a diafiltration technique is carried out on antarctic water and snow samples, characterised by low humic compound content (0.1-0.8 mg/l). Results are compared with those of FA purified with the dialysis technique that, together with ion-exchange resins, performs an often used purification process. With the adopted procedure it is possible to minimise the high content of inorganic salts deriving in part from the isolation method XAD-8 adopted, as shown by FTIR, elemental and thermogravimetric analysis.

The structural composition of humic compounds as indicator of organic carbon sources.

Various analytical techniques ((13)C-NMR, FTIR, elemental analysis) have been used to study the structures of humic compounds present in the sediments of Martignano lake located 50 km from Roma city (Italy). The total amount of humic compounds present in the upper layer of sediments is practically constant; instead, considering humic (HA) and fulvic acids (FA) separately, it can be noticed that while HA increase remarkably from A(1) to A(3), FA diminish, probably as a result of the continuous transformation of algal debris, present in large amount in A(1), from compounds which are in an early stage of decomposition to more highly degraded organic matter. In deeper layers the percentage both of HA and FA is constant and slightly lower than that found in the upper layer, except for two sampling points. In these stations the amount of both HA and FA are very high and the carbohydrate peak areas of HA and FA increase along with the depth, reflecting the presence of a well localized source of organic carbon or different environmental conditions.

Characterization of the organic component of a sludge.

Two sludges of different origin (urban sludge and brewery sludge) have been characterized by fractionating the organic content into five parts (by using acids and bases), followed by multiple-technique examination of each fraction. The techniques used included chemical analysis, thermal analysis, infrared spectrometry and (13)C-NMR spectrometry. This approach successfully distinguished between sludge compositions.

Differential pulse polarographic determination of arsenic, selenium and tellurium at mug levels.

An analytical method, based on differential pulse polarography, for determination of arsenic, selenium and tellurium in solid matrices, is described. The method involves decomposition of the matrix with a mixture of nitric, perchloric and hydrofluoric acid, isolation of tellurium from the other analytes by liquid-liquid extraction (from 4M hydrochloric acid with methyl isobutyl ketone), and determination of the analytes. Tellurium is determined separately, and arsenic is determined in the same solution as selenium after determination and oxidation of the selenium and addition of catechol. Graphitized carbon black and chelating resin were used to eliminate the organic solvent in the aqueous solution and avoid interferences due to the other metals of the matrix. The decomposition, the influence of each analyte on the determination of the others, and the extraction process were given particular attention. The method is characterized by >96% recovery, with a relative standard deviation ranging from 2 to 10% at ppm levels.

Adsorption of phenols by papermill sludges.

In this paper we studied the sorption capacity of paper mill sludges for phenols. Phenol, 2-chlorophenol (2-CP), 3-chlorophenol 3-CP). 4-chlorophenol (4-CP), 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2.4-dichlorophenol (2,4-DCP), 3,4-dichlorophenol (3,4-DCP) 3,5-dichlorophenol (3,5-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) were chosen for the sorption tests. Kinetic experiments showed that substituted-phenol sorption on papermill sludge was rapid (equilibrium was reached after 3 h); conversely, the time taken by the phenol to reach equilibrium conditions was 260 h. Experimental data showed that particle diffusion was involved in the sorption process but was not the only rate-limiting mechanism; several other mechanisms were involved. The adsorption isotherms showed the following order of retention capacity of papermill sludge: 2-NP = 4-NP < < 2-CP < phenol < 4-CP < or = 3-CP < 2,4 DCP<3,4 DCP=2,4,5 TCP<3,5 DCP. In all cases the experimental data showed a good fit with the Hill equation. which is mathemratically equivalent to the Langmuir-Freundlich model obtained by assuming that the surface is homogeneous, and that the adsorption is a cooperative process influenced by adsorbate-adsorbate interactions.

Characteristics of different molecular weight fractions of organic matter in landfill leachate and their role in soil sorption of heavy metals.

We have characterised two kinds of municipal landfill leachates derived from 'old' and 'young' municipal waste landfills on the basis of the molecular weight distribution of the constituents, taking into account that the great variety of leachate constituents prevents any evaluation of the fate and of the role played by each component in the environmental impact. In the sample S1 (old leachate), the constituents were distributed over a wider range of molecular weights; high molecular weight fractions were present. In sample S2 (young leachate), the fractions are actually narrower at the lower molecular weights. The high molecular weight fractions of old leachates are found to be complex structures formed by condensed nuclei of carbons substituted by functional groups containing nitrogen, sulphur and oxygen atoms; the low molecular weight fractions of leachates are, instead, characterised by linear chains substituted by oxygenated functional groups such as carboxyl and/or alcoholic groups. After characterising each fraction we studied the role played by these fractions in the soil's capability for retaining heavy metals [copper (Cu) and cadmium(Cd)]. The Cd uptake increases only on the soil treated with sample S1 characterised by a higher pH value and by the presence of high molecular weight fractions. The Cu uptake also increases on the soil treated with sample S2, characterised by the sole presence of low molecular weight fractions. On the other hand, the metal adsorption tests performed on soil treated with the single fractions show that the amount of Cu and Cd retained by soil treated with the high molecular weight fractions of sample does not increase after 72 h of treatment and that the amount of Cu retained by the low molecular weight fractions of sample S1 and by the fractions of sample S2 increases, but does not justify the amount retained by soil treated with the total leachates.

Metal ion removal from water by sorption on paper mill sludge.

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.

Municipal landfill leachate-soil interactions: a kinetic approach.

On investigating the effects of municipal landfill leachates on soils, it is found that the adsorption of landfill leachate constituents creates a "new" soil surface able to enhance heavy metal uptake. In particular, the treatment of soil with the total leachates led to an increase in its metal retention capability that was much higher than for each individual fraction. Results show that the leachate sorption on soil is regulated by the presence of leachate constituents with low molecular weight cut-off since these fractions are able to "accelerate" the sorption of higher molecular weight fractions. The rapidly sorbed lower molecular weight fractions create a different soil surface that is able to accommodate the high molecular weight constituents.

Changes in copper, lead and zinc concentrations in plants from paper mill sludge-treated soils.

Effects of paper mill sludge addition on the availability of metals were studied on different soils both laboratory and naturally polluted; copper, lead and zinc concentrations were determined in Hordeum Distichum plants grown on the untreated and on sludge-treated soils. In some case a decrease of metal concentration is observed on sludge-treated soils; these results are consistent with the reduction of metal mobile forms in the soil, before plant growth. The decrease of metal availability in sludge-treated soils may be related with the pH value of the soil after sludge addition.