Influence of Rhizophagus irregularis inoculation and phosphorus application on growth and arsenic accumulation in maize (Zea mays L.) cultivated on an arsenic-contaminated soil.

Southern Tuscany (Italy) is characterized by extensive arsenic (As) anomalies, with concentrations of up to 2000 mg kg soil(-1). Samples from the location of Scarlino, containing about 200 mg kg(-1) of As, were used to study the influence of the inoculation of an arbuscular mycorrhizal (AM) fungus (Rhizophagus irregularis, previously known as Glomus intraradices) and of phosphorus (P) application, separately and in combination, on As speciation in the rhizosphere of Zea mays on plant growth and As accumulation. Also, P distribution in plant parts was investigated. Each treatment produced a moderate rise of As(III) in the rhizosphere, increased As(III) and lowered As(V) concentration in shoots. P treatment, alone or in combination with AM, augmented the plant biomass. The treatments did not affect total As concentration in the shoots (with all the values <1 mg kg(-1) dry weight), while in the roots it was lowered by P treatment alone. Such decrease was probably a consequence of the competition between P and As(V) for the same transport systems, interestingly nullified by the combination with AM treatment. P concentration was higher with AM only in both shoots and roots. Therefore, the obtained results can be extremely encouraging for maize cultivation on a marginal land, like the one studied.

Iodine and selenium carry over in milk and cheese in dairy cows: effect of diet supplementation and milk yield.

Iodine and selenium are essential trace elements involved in the regulation of thyroid metabolism and antioxidant status. Two experiments were undertaken on lactating cows to determine the milk concentrations of iodine and selenium, carry over (CO) in milk, the fraction in curdle portion and how milk yield affects the milk iodine and selenium concentrations and CO. Sources of elements were potassium iodide and sodium selenite. In Experiment 1, 12 cows were randomly allotted to three diet groups in a completely randomized design: control group (CTR) - total mixed ration (TMR) containing 1.71 and 0.08 mg/kg dry matter (DM); Group 1 (T1) - TMR plus 23.8 and 2.2 mg; Group 2 (T2) - TMR plus 45.5 and 4.3 mg, respectively, for iodine and selenium. In Experiment 2, 30 cows were allotted to three groups according to milk yield: high (H), average (A) and low (L). Within each group, cows were randomly assigned two levels of iodine and selenium: Level 1: TMR containing 1.55 and 0.15 mg/kg DM; Level 2: TMR plus 47.2 mg and 8.0 mg, respectively, iodine and selenium. In both experiments, individual milk samples were collected and analyzed for iodine and selenium contents. In Experiment 1, Grana Padano cheese was obtained at lab scale and the iodine and selenium fractions in the curd were measured. In Experiment 1, the iodine intake increased (P < 0.001) the concentration and total excretion in milk. The CO increased (P < 0.05) from 16 (CTR) to 27 (T1) and 26% (T2); the sampling time was significant (P < 0.05) with no interaction with treatments. Concentration of selenium in milk was increased (P < 0.05) by treatment and CO decreased (P < 0.01) from 26 (CTR) to 12 (T1) and 9% (T2). The iodine showed a mild enrichment factor in the curdle (about 1.7-fold), whereas selenium enriched five- to sevenfold. In Experiment 2, the level of iodine supplementation affected (P < 0.05) the concentration and total excretion in milk. No effects on milk iodine concentration were related to milk yield or milk yield × treatment interaction; however, the iodine excretion in milk was major (P < 0.05) in higher yielding groups. The iodine CO was affected (P < 0.05) by the milk yield in supplemented groups. The selenium milk concentration and excretion were affected (P < 0.01) by the milk yield, whereas the CO was affected (P < 0.05) by the milk yield and selenium supplementation. Results highlight the possibility of fortification with iodine in milk and selenium in cheese through animal feeding.

Determination of rare earth elements in tomato plants by inductively coupled plasma mass spectrometry techniques.

In recent years identification of the geographical origin of food has grown more important as consumers have become interested in knowing the provenance of the food that they purchase and eat. Certification schemes and labels have thus been developed to protect consumers and genuine producers from the improper use of popular brand names or renowned geographical origins. As the tomato is one of the major components of what is considered to be the healthy Mediterranean diet, it is important to be able to determine the geographical origin of tomatoes and tomato-based products such as tomato sauce. The aim of this work is to develop an analytical method to determine rare earth elements (RRE) for the control of the geographic origin of tomatoes. The content of REE in tomato plant samples collected from an agricultural area in Piacenza, Italy, was determined, using four different digestion procedures with and without HF. Microwave dissolution with HNO3 + H2O2 proved to be the most suitable digestion procedure. Inductively coupled plasma quadrupole mass spectrometry (ICPQMS) and inductively coupled plasma sector field plasma mass spectrometry (ICPSFMS) instruments, both coupled with a desolvation system, were used to determine the REE in tomato plants in two different laboratories. A matched calibration curve method was used for the quantification of the analytes. The detection limits (MDLs) of the method ranged from 0.03 ng g(-1) for Ho, Tm, and Lu to 2 ng g(-1) for La and Ce. The precision, in terms of relative standard deviation on six replicates, was good, with values ranging, on average, from 6.0% for LREE (light rare earth elements) to 16.5% for HREE (heavy rare earth elements). These detection limits allowed the determination of the very low concentrations of REE present in tomato berries. For the concentrations of REE in tomato plants, the following trend was observed: roots > leaves > stems > berries.

The role of natural purified humic acids in modifying mercury accessibility in water and soil.

Contamination of soils with mercury can be a serious problem. It can be mobilized or stabilized by humic substances (HS) containing binding sites with reduced sulfur that can have different binding capacities for CH(3)Hg(+) and for Hg(2+). In this work we investigated the influence of different humic acids (HAs, extracted from lignite, compost, and forest soil) on mercury mobility and availability, both in a model solution and in soil samples from a mercury-polluted region. The technique of diffusive gradients in thin-films (DGT), which is capable of measuring: (i) free metal in solution; (ii) dissociated metal complexes previously mobilized by HA; (iii) mobilized metal-HA complexes that liberate metals by dissociation or by exchange reaction between the metal-HA complexes and the chelating groups on the resin-gel, was used in solutions and soils. The DGT measurements in solution, together with ultrafiltration, allowed estimation of the lability of Hg-HA complexes. Ultrafiltration results were also compared with predictions made by the windermere humic-aqueous model (WHAM). According to both these different approaches, Hg(2+) resulted nearly 100% complexed by HAs, whereas results from ultrafiltration showed that 32 to 72% of the CH(3)Hg(+) was bound to the HAs, with higher values for compost and lower values for forest and Aldrich HA. The DGT-measured mercury in soils was below 0.20 microg L(-1), irrespective of the extent of the contamination. Addition of HA increased the concentration of DGT-measured mercury in soil solution up to 100-fold in the contaminated soil and up to 30-fold in the control soil. The level of the increase also depended on the HA. The smallest increase (about 10 times) was found for lignite HA in both control and contaminated soils. The addition of forest HA gave the largest increases in DGT-measured mercury, in particular for the contaminated soil. Overall, the results demonstrated that DGT can be used for estimating the lability of mercury complexes in solution and for verifying enhanced mercury mobility when HA is added to contaminated soils.

Characterization of mercury species in soils by HPLC-ICP-MS and measurement of fraction removed by diffusive gradient in thin films.

The properties and behaviour of Hg depend on both the oxidation state and the chemical form: the bioavailability, toxicity, persistence and accumulation of mercury in the food web are strongly influenced by chemical speciation. The present work aims to determine the chemical forms of mercury present in soil and to evaluate the fraction of mercury in soil solution available to plants. In order to do this, we analyzed eight samples of contaminated soils with Hg concentrations ranging from 1.31 to 21.7 mg kg(-1), collected from different depths (0-10 and 40-50 cm) close to an abandoned industrial site in Val Basento (southern Italy). Two innovative analytical techniques were used: HPLC-ICP-MS and diffusive gradient in thin films (DGT). The analytical procedure was validated using ERM 580-certified sediment and spiked samples in the case of HPLC-ICP-MS, and by a performance test in the case of DGT. In all samples, the only species found in soil and soil solution was MeHg(+) and Hg(2+). In soil, the MeHg(+)/Hg(tot) ratio ranged from 0.05% to 0.82%; total mercury in soil solution was less than 0.01% of total mercury in soil. The percentage of MeHg(+) in soil solution varied considerably (from 0% to 50%), with a maximum concentration of 0.02 mg L(-1). The root available concentration evaluated by DGT is comparable to the total mercury content of the soil solution measured by HPLC-ICP-MS. The DGT results suggest that all mercury in solution is available for uptake in DGT, and that mercury is supplied from soil to solution. However, for all samples the soluble and root available (DGT-labile) fractions of mercury are generally very low with respect to the total mercury concentration. This study confirmed that both HPLC-ICP-MS and DGT techniques are suitable tools for the estimation of Hg root availability and in assessing the risk from contaminated soils.

Comparison of different analytical procedures in the determination of trace elements in lichens.

A BCR standard reference material of lichen (CRM 482) was used to validate an analytical procedure consisting of a microwave oven digestion associated with ICP-OES, ICP-MS and GFAAS techniques for the analysis of trace elements (Al, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn) in biomonitor samples. Two different acid mixtures were used: (a) 7 ml of HNO3, 1 ml of H2O2; (b) 7 ml of HNO3, 1 ml of H2O2 and 200 microl of HF; all digestions were carried out using 100-250 mg samples brought to a final volume of 50 ml. The validation of the procedure was carried out by two laboratories in terms of accuracy and precision; the former was estimated as percentage recovery by comparing experimental data with certificate values; the latter evaluated according to ISO standard 5725. Real lichen samples were analysed too with the procedures above described. In certified CRM 482 and real lichen samples the procedure with HF showed higher recovery values for Al, Ti, V, Ba and Fe than the procedure without HF. For all the other elements the two procedures gave comparable results both in terms of accuracy and precision. The recovery obtained with HF procedure for all the elements was generally better than 90-103%.