Characterization of As-polluted soils by laboratory X-ray-based techniques coupled with sequential extractions and electron microscopy: the case of Crocette gold mine in the Monte Rosa mining district (Italy).

Arsenic concentration and distribution were studied by combining laboratory X-ray-based techniques (wavelength dispersive X-ray fluorescence (WDXRF), micro X-ray fluorescence (µXRF), and X-ray powder diffraction (XRPD)), field emission scanning electron microscopy equipped with microanalysis (FE-SEM-EDX), and sequential extraction procedure (SEP) coupled to total reflection X-ray fluorescence (TXRF) analysis. This approach was applied to three contaminated soils and one mine tailing collected near the gold extraction plant at the Crocette gold mine (Macugnaga, VB) in the Monte Rosa mining district (Piedmont, Italy). Arsenic (As) concentration, measured with WDXRF, ranged from 145 to 40,200 mg/kg. XRPD analysis evidenced the presence of jarosite and the absence of any As-bearing mineral, suggesting a high weathering grade and strong oxidative conditions. However, small domains of Fe arsenate were identified by combining µXRF with FE-SEM-EDX. SEP results revealed that As was mainly associated to amorphous Fe oxides/hydroxides or hydroxysulfates (50-80%) and the combination of XRPD and FE-SEM-EDX suggested that this phase could be attributed to schwertmannite. On the basis of the reported results, As is scarcely mobile, even if a consistent As fraction (1-3 g As/kg of soil) is still potentially mobilizable. In general, the proposed combination of laboratory X-ray techniques could be successfully employed to unravel environmental issues related to metal(loid) pollution in soil and sediments.

Total As and As Speciation in Italian Rice as Related to Producing Areas and Paddy Soils Properties.

Rice and rice-based foodstuffs are important pathways for inorganic As dietary intake. This work shows a detailed picture of As content and speciation in Italian rice, which contributes to more than one-half of the European production, and addresses the role of soil chemistry and agronomic management on As concentration in rice grain, in view of ameliorative strategies. The mean total As content in Italian white rice was 155 ± 65 µg kg-1 with significant differences among producing areas, while the mean inorganic As was 102 ± 26 µg kg-1, largely below the E.U. limit of 200 µg kg-1 for white rice, although part of the production would not be suitable for baby food production, which requires less than 100 µg kg-1 of inorganic As. The differences in As content and speciation in rice among the studied areas resulted from the complex interactions of soil, plant, and anthropic factors. Among others, Si nutrition seemed to play a key role in regulating As transfer from soil to plant.

Potential phosphorus and arsenic mobilization from Bangladesh soils by particle dispersion.

Besides dissolution, particle dispersion and mobilization can substantially contribute to element transfer from soils to waters. The dispersibility of the fine particulate and the associated potential losses of P and As from Bangladesh soils of the Ganges and Meghna floodplains have been evaluated with a simple dispersion test. The dispersible fraction was greater for the coarse-textured soils from the Meghna floodplain and increased with particle charge density. Particulate phosphorus (PP) and As (PAs) were the dominant forms in the dispersion, dissolved P and As being scarce to negligible. The PP and PAs were related to the amount of dispersed particulate, oxalate-extractable iron and, respectively, to the water-extractable P or phosphate-extractable As. Although reductive dissolution is reported as the main mechanism of As mobilization during prolonged monsoon flooding, the transfer in particulate form could potentially represent a major pathway for P and As transfer from soils to waters in oxic environments after sudden, extreme events. Since the frequency of extreme rainfall and floods is increasing because of the climate changes, and the intensified land cultivation is enhancing soil disturbance, larger contributions of particulate runoff to element migration from soils to waters could be expected in the future.

Release of phosphorus under reducing and simulated open drainage conditions from overfertilised soils.

Does removal of cations from soil solution during soil reduction stimulate phosphorus (P) release? An ion-exchange resin system was employed to provide a sink during the incubation of twelve soils under fully reducing conditions. This experimental design was considered to better simulate the loss of ions likely to occur under field conditions than more routine batch type closed extraction systems where solutes build-up in the extract solution. The small solute concentrations that remain in the equilibrating solution suggest the mixed resin system acted as an effective sink over the whole experimental period. By maintaining a small P concentration the resin system mimics soil drainage conditions and encourages P release from soil. Measurement of soil P forms by sequential extraction after the incubation period indicated an increase in the amorphous forms present. Here we show that even if the P-containing solution is retained by the soil, the potential for a subsequent P loss is increased under aerobic conditions. The management of drainage systems should try and avoid the onset of anaerobic conditions. Eventually, magnesium- and calcium-based precipitation products could recapture P from drains recycling it in topsoils as fertilizer.

Fertilization strategies affect phosphorus forms and release from soils and suspended solids.

The release of phosphorus from soils in surface runoff is strongly influenced by fertilizer inputs and contributes significantly to agriculturally driven eutrophication. This work evaluated the forms and availability of P in bulk soils and suspended solids (SS) produced by a water dispersion test that mimics the action of rain events and/or irrigation. This test was applied on soils cultivated with maize and fertilized with mineral N, P, and K (NPK); mineral P and K (PK); bovine slurry and P (S); or manure and P (M) for 15 yr. The P surplus in the treated soils was in the order NPK < PK < S < M. Forms and availability of P were analyzed in bulk soils, and their respective SS (<20 µm) by the Hedley sequential P fractionation method and the isotopic exchange kinetics. The labile forms increased according to P surplus and represented up to 15 and 25% of total P in the bulk soil and in the SS, respectively, indicating a selective enrichment of the more labile P forms in the erodible particles. Exchangeability of P from SS was rapid and intense as a result of a shift of P solution equilibrium at the increased water/solid ratio and a larger accumulation of more labile P in the detached particles than in the bulk soil. Phosphorus saturation of iron and aluminum oxides and the enrichment of fertilizer-derived P salts in the suspended solids control P forms and exchangeability for mineral fertilizer treatments, whereas in M soil carbon content assumed a key role.

Are agricultural soils under a continental temperate climate susceptible to episodic reducing conditions and increased leaching of phosphorus?

Soil science research has probably underestimated the significance that short-term, episodic cycles of reduction and oxidation has had on phosphorus (P) reactivity. Here, the effects of eleven pulsed reduction-oxidation (including wet-dry) cycles on soil P dynamics are compared for 12 soils having contrasting properties and all overfertilised with respect to P. The laboratory based incubation conditions attempted to simulate transient waterlogging of the soil profile and involved repeated sampling and analysis of both the solution and solid phase P forms. An initial increase in P concentration in solution that occurred up to and including the fourth full cycle was followed by a sharp decline in concentration for all but one soil. Accompanying changes in the main extractable forms of P, which appeared to be cumulative, could be summarised as a general decline in the organic P fraction and an overall increase in amorphous associated inorganic forms of P. The fact that up to 60% of the total soil P was demonstrated to change its sensitivity for a particular extractant suggests that these operationally defined P forms are susceptible to transformation as a consequence of changing environmental conditions. There was also a suggestion that certain of the changes in P forms were irreversible. While the laboratory conditions imposed do represent extreme conditions the soils only experienced cyclic changes in their moisture regime. If timing and frequency of intense precipitation events are likely to increase, as predicted in many climate change scenarios, then these results suggest that the effects of episodic redox pulses may have implications for P cycling in agricultural soils.

Variability in the mobilization of sediment and phosphorus across 13 European soils.

The objectives of this study were to examine the variability in mobilization and transport of primary particles and associated total phosphorus (TP) in sediments eroded by overland flow from 13 European arable soils and to consider the empirical support for more process-based alternatives to modeling phosphorus (P) transfers. The 13 soils were subjected to simulated rainfall in laboratory experiments. Rainfall was applied to a soil flume (0.5 x 0.25 m) for 30 min at intensity of 60 mm h(-1), and all overland flow generated during this period was collected. Two simulations were performed 5 d apart. The soils generated a wide range of overland flow (13.3-26.9 mm) and sediment (1.1-16.9 g). The sediments from the experiments were enriched with medium silt particles (6-20 mum). Except for one soil in the second simulation, all of the study soils produced overland flow sediments (OFS) that were enriched with P (TP 976-3884 mg kg(-1), P enrichment ratio 0.92-4.42). Sediment TP was positively correlated (P < 0.05) with the sediment clay contents for both simulation events, and sediment total P enrichment was negatively correlated with soil TP. Attempts to reconstruct the TP content of sediments from TP analysis of the soil particle size fractions yielded significant (P < 0.05) relationships between reconstructed and measured TP values. However, the reconstructed TP values were consistently lower than the measured sediment TP contents, indicating that further improvements to measurement techniques are required if physically based modeling of P transport in overland flow is to be successful at small scales.

Fate of arsenite and arsenate in flooded and not flooded soils of southwest Bangladesh irrigated with arsenic contaminated water.

In Bangladesh and West Bengal, India, tons of arsenic are added every year to wide extensions of agricultural soils after irrigation with arsenic polluted groundwater, and the fate of the added arsenic in these water-soil environments is not yet clear. This work was aimed to investigate the accumulation and potential release of arsenite [As(III)] and arsenate [As(V)] in two adjacent soils of Bangladesh, irrigated with arsenic contaminated groundwater and cultivated under flooded or not flooded conditions. Both soils showed a scarce As accumulation, in spite of a good adsorption capacity, higher for As(III) than for As(V). The poorly ordered Fe oxides dominated As adsorption in the topsoil of the flooded soil, whereas the crystalline forms were more important in the well aerated soil. A high percentage of the native arsenic was exchangeable with phosphate and the freshly added arsenate or arsenite were even much more mobile. In our experimental conditions, the high As mobility was not dependent on the surface coverage, and, in the flooded soil, 60-70% of the freshly added arsenite or arsenate were desorbed with an infinite sink method, while in the not flooded soil arsenate was less desorbed than arsenite. Depending on their characteristics, some soils, in particular when cultivated under flooded conditions, can represent only a temporary sink for the added As, that can be easily released to waters and possibly enter the food chain from the water-soil system.

Soil variables for predicting potential phosphorus release in Swedish noncalcareous soils.

The accumulation of P in agricultural soils due to fertilization has increased the risk of P losses from agricultural fields to surface waters. In risk assessment systems for P losses, both P release from soil to solution and transport mechanisms need to be considered. In this study, the overall objective was to identify soil variables for prediction of potential P release from soil to solution. Soils from nine sites of the Swedish long-term fertility experiment were used, each with four soil P levels. Phosphorus extractable with CaCl2 was used as an estimate of potential P release from soil to solution. Ammonium lactate-extractable phosphorus (P-AL) or NaHCO3-extractable phosphorus (Olsen P) could not be used alone for prediction of potential P release since soils with high phosphorus sorption capacity (PSC) released less P than soils with low PSC at the same soil test phosphorus (STP) level. Degree of phosphorus saturation (DPS) was calculated as Olsen P or P-AL as a percentage of PSC derived from P sorption isotherms or from Fe and Al extractable in ammonium oxalate. The CaCl2-extractable total phosphorus (CaCl2-TP) was exponentially related to these DPS values (r2 > or = 0.79). The CaCl2-TP was also linearly related to ratios between Olsen P or P-AL and a single-point phosphorus sorption index (PSI; r2 > or = 0.86). These ratios, which are easily determined and gave good correlations with CaCl2-TP, seemed to be the most useful estimates of potential P release for risk assessment systems.