Jean-Claude Bollinger

Contamination of vineyard soils with fungicides: a review of environmental and toxicological aspects.

The contamination of agricultural soils with inorganic (Cu-based) and organic pesticides (including their residues) presents a major environmental and toxicological concern. This review summarizes available studies published on the contamination of vineyard soils throughout the world with Cu-based and synthetic organic fungicides. It focuses on the behavior of these contaminants in vineyard soils and the associated environmental and toxicological risks. The concentrations of Cu in soils exceed the legislative limits valid in the EU in the vast majority of the studied vineyards. Regarding the environmental and toxicological hazards associated with the extensive use of fungicides, the choice of fungicides should be performed carefully according to the physico-chemical properties of the soils and climatic and hydrogeological characteristics of the vine-growing regions.

Arsenite oxidation and arsenate determination by the molybdene blue method

Based on the similarity in properties of arsenate and phosphate, the colorimetric method using the molybdene blue complex was tested in order to determine low As(V) concentration in waters. The influence of complex formation time, daylight, temperature and competitive anions (silicate and sulphate) upon complex formation was determined. Optimal complex formation was reached in 1 h at 20+/-1 degrees C and was slightly favoured when developed in daylight. The formation rate declined with decreasing reaction temperature and no influence of any of the competitive anions tested (at concentrations usually found in natural waters of granitic areas) was noted. The detection limit of this method was 20 mug As(V) l(-1). This simple, fast and sensitive arsenic determination method is suitable for field analysis, especially for waters containing low levels of phosphate and organic matter. Through arsenate determination, this colorimetric method allowed the arsenite oxidation efficiency of five common industrial oxidants to be compared. H(2)O(2) and MnO(2(s)) were not considered as effective oxidants as a high excess was necessary to ensure As(III) oxidation. NaOCl and KMnO(4) were promising oxidants as they allowed complete arsenite oxidation with a small excess for NaOCl or even less than the electron stoichiometric ratio in the case of KMnO(4). FeCl(3) was the most effective oxidant among the reagents tested here.

Calcium carbonate solubility: a reappraisal of scale formation and inhibition

Considerable disparity exists in the published thermodynamic data for selected species in the Ca(2+) /CO(2)/H(2)O system near 25 degrees C and 1 atm pressure. Some authors doubt the significance of CaCO(3)(0)aq) complexes although there is experimental evidence of their occurrence. Evaluation of all the published experimental and estimated data for aqueous calcium carbonate species confirms that the consistent set of constants given by Plummer and Busenberg in 1982 is the best available, and suggests a formation constant log beta = 3.22 for CaCO(3)(0)(aq). This value was confirmed by additional experimental data and calculations using a specially developed computer program. The solubility s and solubility product K(s) are critically evaluated for each solid polymorph (amorphous CaCO(3), ikaite, vaterite, aragonite and calcite) using a hydrated ion pair model and we give coherent explanations for the calcium carbonate precipitation/dissolution process and the existence of supersaturated waters. The practical cases of scale formation and its inhibition by phosphonate-type compounds are discussed and explained with the same model, taking into account the CaCO(3)(0)(aq) species.

Arsenic removal by a waste metal (hydr)oxide entrapped into calcium alginate beads.

In this work, a solid waste material from an electroplating industrial plant has been investigated for As(III) and As(V) sorption. This sorbent, a mixture of mainly Fe(III) and Ni(II) (hydr)oxides, has been used both in its native form and entrapped in calcium alginate. The effect of sorbent concentration in the gel bead, solution pH, contact time and As(III) and As(V) concentration on sorption has been studied. Furthermore the effect of the gel matrix has been investigated. A 10% (w/v) of (hydr)oxide in the gel beads was found to provide both spherical beads shape and good sorption performance. Solution pH was found to exert a stronger influence in As(V) than in As(III) sorption. The optimum pH range resulted to be within 5-10 for As(III) and within 6-9 for As(V). Taking into account these results, pH 8 was chosen for further sorption experiments. Equilibrium was reached after 48 h contact time for the studied systems. Kinetics data of both As(III) and As(V) onto native (hydr)oxide (O) and entrapped in calcium alginate beads (10% O-CA) were successfully modelled according to pseudo-first and pseudo-second order equations. Sorption equilibrium data were evaluated by the Langmuir isotherm model and the maximum capacity q(max) were 77.4 and 126.5 mg g(-1) for As(III) on O and 10% O-CA, and 26.8 and 41.6 mg g(-1) for As(V) on O and 10% O-CA, respectively. The entrapment of the (hydr)oxide in a calcium alginate gel matrix improved the As(III) and As(V) sorption by 60%.

Removal of heavy metals in industrial wastewaters by ion-exchanger grafted textiles

Abstract A special class of grafted textiles was studied in order to remove heavy metals from industrial wastewaters. Three cation-exchanger textiles (CET) were tested in a batch reactor, each carrying carboxylate (RCOO−, Na+), sulfonate (RSO3−, Na+) or phosphate (ROPO32−, 2Na+) functional groups. The study of their behaviour towards Cu(II) and Cd(II) was carried out as a function of time (exchange kinetics) and at equilibrium with increasing metal concentrations (exchange isotherms). After determining the exchange capacities and selectivity coefficients of CET, the influence of different parameters (the counter-ion and functional group nature, the metal concentration, the presence of different competitors in the solution) on the removal of Cu(II) and Cd(II) was shown. The optimal use conditions of CET were therefore well defined and compared with those of conventional resins. Finally, desorption studies were performed with various regenerating solutions in order to determine the best conditions for textile regeneration and an optimal heavy metal concentration. These cation-exchanger textiles offer an interesting alternative for water treatment by ion-exchange technique.

Divalent cations speciation with three phosphonate ligands in the pH-range of natural waters

AMP and HEDP complexation constants for seven divalent cations (Ca, Cu, Cd, Fe, Ni, Pb and Zn) have been determined by acid-base titrations at 25 +/- 0.5 degrees C, at constant ionic strength (0.1 M KNO(3)) with Martell and Motekaitiss computer programs. Speciation diagrams enable us to compare AMP, HEDP and TPP complexing properties. AMP complexes more strongly all seven divalent cations than HEDP and TPP, which have similar ligand behavior. Among the divalent cations studied here, the ligands have lowest affinity with calcium and usually higher with copper. In all the cation/ligand systems, the major species are ML and MHL which are charged species. The uncharged ionic species Ca(2)Y(0), CaH(4)X(0) and CdH(2)Y(0) (H(6)X = AMP and H(4)Y = HEDP) which can potentially exist in solid phase, cannot be neglected. Moreover hydroxide complexes have to be taken into consideration in the complexation constant determinations and in the environmental impact.

Effect of organic matter on arsenic removal during coagulation/flocculation treatment.

The aim of this study is to evaluate the influence of organic matter on arsenic removal by coagulation/flocculation on both a model water with low mineral content and a natural water sample. Ferric chloride was used as coagulant at concentrations avoiding the preoxidation step usually required to oxidize As(III) and increase its removal. Arsenic removal was accomplished by combining evaluation of arsenic residual concentrations and speciation analysis with zeta potential measurements. A preliminary study evaluated the influence of coagulant dose, coagulation pH, and organic matter on As(III) and As(V) removal. The main conclusions were: (i) As(III) removal depended on coagulant dose and on the number of sites available on hydroxide surfaces rather than on coagulation pH; (ii) As(V) removal depended on the zeta potential of colloidal suspension and was more influenced than As(III) by coagulation pH and the presence of organic matter; (iii) organic matter removal followed As(V) removal. This allowed determination of adsorption as the main mechanism occurring during As(V) and organic matter removal and supposing precipitation/coprecipitation as an important As(III) removal mechanism. Adsorption on preformed ferric hydroxide flocs experiments allowed then confirmation of these hypotheses.

Adsorption of copper, cadmium, lead and zinc onto a synthetic manganese oxide

Due to its simple and inexpensive synthesis, a new amorphous hydrous manganese oxide (AMO) has been studied as a possible chemical stabilizing agent for soils contaminated with metals. Preliminary experiments evaluating the stability of AMO in pure water have reported only minor dissolution (5.70% and 0.24% depending on the w/v ratio). Sorption kinetics have shown fast metal adsorption, especially for Pb. The sorption capacities of AMO for Cu, Cd, Pb, and Zn have been described and compared with synthetic birnessite for pH 4 and 5.5. Both oxides show similar sorption capacities at pH 4 despite the fact that birnessite characteristics (pH of zero point charge, specific surface area and cation exchange capacity) are more favorable for metal sorption. Moreover, the pH adsorption-edges show that the AMO is more pH-dependent than birnessite.

Optimization of a GFAAS method for determination of total inorganic arsenic in drinking water

The new 10mugl(-1) arsenic standard in drinking water has been a spur to the search for reliable routine analytical methods with a limit of detection at the mugl(-1) level. These methods also need to be easy to handle due to the routine analyses that are required in drinking water monitoring. Graphite furnace atomic absorption spectrometry (GFAAS) meets these requirements, but the limit of detection is generally too high except for methods using a pre-concentration or separation step. The use of a high-intensity boosted discharge hollow-cathode lamp decreases the baseline noise level and therefore allows a lower limit of detection. The temperature program, chemical matrix modifier and thermal stabilizer additives were optimized for total inorganic arsenic determination with GFAAS, without preliminary treatment. The optimal furnace program was validated with a proprietary software. The limit of detection was 0.26mugAsl(-1) for a sample volume of 16mul corresponding to 4.2pgAs. This attractive technique is rapid as 20 samples can be analysed per hour. This method was validated with arsenic reference solutions. Its applicability was verified with artificial and natural groundwaters. Recoveries from 91 to 105% with relative standard deviation <5% can be easily achieved. The effect of interfering anions and cations commonly found in groundwater was studied. Only phosphates and silicates (respectively at 4 and 20mgl(-1)) lead to significant interferences in the determination of total inorganic arsenic at 4mugl(-1).

Column leaching of chromium and nickel from a contaminated soil using EDTA and citric acid

This study investigates the column leaching of a soil contaminated mainly with Cr and Ni by using two chelants: citric acid (biodegradable) and EDTA (non-biodegradable) followed with water rinse. The chelants lead to Cr and Ni leaching, in addition to major elements (Ca, Fe, Mg, Al, Mn and Zn) showing the dissolution of soil mineral constituents. EDTA leaches more major elements and Ni than citric acid related to the respective stability of metal-chelant complexes; citric acid leaches more Cr than EDTA, certainly because of a substitution reaction with Cr(VI). In the case of alternating chelant/water applications, leaching occurs during the chelant applications, but also during water applications. In the case of chelant/water applications followed by continuous water application, both Cr and Ni leach over time. This increased mobility could be due to the residual chelant present in soil as well as to the dissolution/mobilization of mineral or organic soil fractions.