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The sulfate sorption was studied on Andisols with variable mineralogical composition and low organic matter content in presence and absence of phosphate or malate ligands at different pH. Crystalline clay mineralogy was similar for all the studied samples, except for the 2C horizon of the pedon 2, which did not show crystalline minerals. The soil samples showed content of allophane ranging from 16% to 42%. The sulfate adsorption decreased when descending the first 3 horizons (A1, 2A2 and 3Bw1) of the pedon 1. This behavior was attributed to the decreasing organic carbon content. At different pH sulfate sorption was drastically decreased by increasing the pH from 4.0 to 7.0, precisely by 80% for sample 5 to 100% for sample 1. Experiments on the competitive sorption of phosphate and sulfate on volcanic soils were carried out. Sulfate sorption was reduced even in the presence of low concentrations of phosphate ions (phosphate/sulfate molar ratio << 1). Sulfate sorption was influenced by many factors as the organic carbon content, pH, the mineralogical composition of soil samples and the order of sulfate and phosphate addition into the soils. Sulfate competes with phosphate particularly when added before phosphate and at low pH values (pH < 4.5). Phosphate more than malate affected the kinetics of sulfate sorption onto a volcanic soil containing a large amount of allophanic materials La adsorción de sulfato fue estudiada en Andisoles con una composición mineralógica variable y bajo contenido de materia orgánica en presencia y ausencia de fosfato o malato a diferentes pH. La mineralogía de las arcillas cristalinas fue similar para todos las muestras estudiadas, excepto para el horizonte 2C del pedon 2, la cual no mostró minerales cristalinos. Las muestras de suelo presentaron contenidos de alofán en el rango de 16 a 42 %. La adsorción de sulfato incrementó al descender los primeros 3 horizontes (A1, 2A2 and 3Bw1) del pedon 1. Este comportamiento fue atribuído a la disminución del contenido de carbono orgánico. A diferentes pH la adsorción de sulfato fue drásticamente disminuída el aumento del pH desde 4,0 a 7,0, desde un 80 % para la muestra 5 a 100 % para la muestra 1. La adsorción de sulfato fue reducida incluso en presencia de bajas concentraciones de iones fosfato (razón molar fosfato/sulfato 1). Experimentos de adsorción competitiva de fosfato y sulfatos fueron realizado en suelos volcánicos. La adsorción de sulfato fue influenciada por muchos factores, como el contenido de materia orgánica, pH, composición mineralógica de los suelos y el orden de adición de sulfato y fosfato en los suelos. Sulfato compite con fosfato particularmente cuando es adicionado antes que fosfato y a bajos valores de pH (pH 4,4). Fosfato más que malato afectó la cinética de la adsorción de sulfato en un suelo volcánico conteniendo una gran cantidad de materiales alofánicos

Despite the centrality of staple grains for human well-being, both as a source of nutrients and of toxic ions, there is little understanding of where and how elements vary, and if there are particular elements that correlate. Here, for shop bought polished (white) rice, we comprehensively characterized trace (arsenic species, cadmium, copper, iron, manganese, molybdenum, rubidium and zinc) and macro-nutrients (calcium, chlorine, potassium, phosphorus and sulphur) for grain purchased in 18 countries, across four continents, a total of 1045 samples. This was to investigate if there were any major differences between geographic location and elemental content, and to observe if there were any patterns in elemental distribution. Greatest variation in the median was observed for the non-essential rubidium (15-fold) and arsenic species (fivefold). Rubidium was the highest in the Americas, lowest in Europe, while inorganic arsenic (iAs) and dimethylarsonic acid (DMA) were low for Africa and high in the South American and European continents. The highest concentrations of cadmium were found in Asian samples, and lowest in South America, with variation within these regions. At the extremes of individual counties, China had fivefold higher concentrations than the global median, while Tanzania was fourfold lower than this value. Calcium, potassium, molybdenum and phosphorus were the highest in European and lowest in African grain, though the fold-differences were relatively low, ~ 0.2, while iron was the highest in African grain and lowest in European, Asian and South American grain, with a ~ twofold difference. Selenium was also higher in Africa versus other regions, and copper, manganese and zinc were the highest in American grain. Factor analysis showed that copper, cadmium, molybdenum, rubidium and selenium were strongly associated together, and these element’s factor loadings were diametrically opposed to less tightly associated calcium, chlorine, manganese, potassium, phosphorus and sulphur. Stepwise additions linear region analysis was performed on log-transformed concentrations to investigate cadmium associations in more detail. Selenium was the greatest predictor of cadmium concentration, followed by molybdenum, accounting for over 50% of the contribution to the adjusted R2. Arsenic species were only weakly correlated with other elements. The implications for these findings with respect to dietary nutrition are discussed. Vietnamese rice was notable in being deficient in macro- and micro-nutrients while also being elevated in cadmium at a median of 0.02 mg/kg, with China though still having a median that is ~ 2.5-fold this concentration. These Chinese concentrations are of particular concern as the 75th percentile for China is 0.1 mg/kg, a value that triggers regulatory action for rice products.

Green, Andy J. et al., One of cadmium’s major exposure routes to humans is through rice consumption. The concentrations of cadmium in the global polished (white), market rice supply-chain were assessed in 2270 samples, purchased from retailers across 32 countries, encompassing 6 continents. It was found on a global basis that East Africa had the lowest cadmium with a median for both Malawi and Tanzania at 4.9 μg/kg, an order of magnitude lower than the highest country, China with a median at 69.3 μg/ kg. The Americas were typically low in cadmium, but the Indian sub-continent was universally elevated. In particular certain regions of Bangladesh had high cadmium, that when combined with the high daily consumption rate of rice of that country, leads to high cadmium exposures. Concentrations of cadmium were compared to the European Standard for polished rice of 200 μg/kg and 5% of the global supply-chain exceeded this threshold. For the stricter standard of 40 μg/kg for processed infant foods, for which rice can comprise up to 100% by composition (such as rice porridges, puffed rice cereal and cakes), 25% of rice would not be suitable for making pure rice baby foods. Given that rice is also elevated in inorganic arsenic, the only region of the world where both inorganic arsenic and cadmium were low in grain was East Africa.

Arsenic in rice grain is dominated by two species: the carcinogen inorganic arsenic (the sum of arsenate and arsenite) and dimethylarsinic acid (DMA). Rice is the dominant source of inorganic arsenic into the human diet. As such, there is a need to identify sources of low-inorganic arsenic rice globally. Here we surveyed polished (white) rice across representative regions of rice production globally for arsenic speciation. In total 1180 samples were analysed from 29 distinct sampling zones, across 6 continents. For inorganic arsenic the global $$\tilde{x}$$ x ~ was 66 μg/kg, and for DMA this figure was 21 μg/kg. DMA was more variable, ranging from $$\tilde{x}$$ x ~ $$\tilde{x}$$ x ~

Biomass-derived biochar is considered as a promising heavy metal adsorbent, due to abundance of polar functional groups, such as carboxylic, hydroxyl, and amino groups, which are available for heavy metal removal. The aims of this study were to evaluate the effectiveness of an orchard pruning-derived biochar in removing some heavy metals (through the evaluation of isotherms) and to study water dynamics at the solid-liquid interface as affected by heavy metal adsorption (through an innovative nuclear magnetic resonance (NMR) relaxometry approach). Both isotherms and NMR spectra revealed that Pb and Cr showed a good affinity for the biochar surface (Pb > Cr), while Cu was less affine. Accordingly, higher amounts of Pb and Cr were adsorbed by biochar as compared to those of Cu in the single systems. In binary systems (i.e., when two metals were applied simultaneously), Pb showed the highest inhibition of the adsorption of the other two metals, whereas the opposite was evidenced when Cu was used; the competitive adsorption was also strongly influenced by the metal residence time on biochar surface. In ternary systems (i.e., when all metals were applied simultaneously), even in the presence of high amounts of Pb and Cr, considerable adsorption of Cu occurred, indicating that some biochar adsorption sites were highly specific for a single metal.

Rice is comparatively efficient at assimilating inorganic arsenic (Asi), a class-one, non-threshold carcinogen, into its grain, being the dominant source of this element to mankind. Here it was investigated how the total arsenic (Ast) and Asi content of Italian rice grain sourced from market outlets varied by geographical origin and type. Total Cr, Cd Se, Mg, K, Zn, Ni were also quantified. Ast concentration on a variety basis ranged from means of 0.18 mg kg(-1) to 0.28 mg kg(-1), and from 0.11 mg kg(-1) to 0.28 mg kg(-1) by production region. For Asi concentration, means ranged from 0.08 mg kg(-1) to 0.11 mg kg(-1) by variety and 0.10 mg kg(-1) to 0.06 mg kg(-1) by region. There was significant geographical variation for both Ast and Asi; total Se and Ni concentration; while the total concentration of Zn, Cr, Ni and K were strongly influenced by the type of rice.

We have studied the uptake and distribution of arsenic (As) and phosphorus (P) in roots, shoots and berries of tomato plants, grown on uncontaminated soil, irrigated with As-contaminated solutions at four concentrations (0, 0.5, 2 and 4 mg L -1 ), in presence or absence of P fertilization.The biomass of tomato plants decreased with increasing As concentration in irriga-tion water, especially tomato berries. In addition, the reduction of biomasses was significantly greater in plants non-fertilized with P. The beneficial effect generated with the P addition indicated that this nutrient played an important role in alleviating As toxicity in tomato plants. The higher the As concentration in irrigation water the higher the As concentration in plant tissues; most of the As absorbed by plants was accumulated in their roots. Phosphorus application has allowed to reduce As trans-location toward tomato berries, enhancing plant P status. These observations may be useful for certain areas of the World, in which As-contaminated waters are used for agricultural purposes.Keywords: tomato, arsenic, uptake, phosphorus fertilization, contamination.

The influence of compost on the growth of bean plants irrigated with As-contaminated waters and its influence on the mobility of As in the soils and the uptake of As (as NaAs III O 2 ) by plant components was studied at various compost application rates (3·10 4 and 6·10 4 kg ha −1 ) and at three As concentrations (1, 2 and 3 mg kg −1 ). The biomass and As and P concentrations of the roots, shoots and beans were determined at harvest time, as well as the chlorophyll content of the leaves and nonspecific and specifically bound As in the soil. The bean plants exposed to As showed typical phytotoxicity symptoms; no plants however died over the study. The biomass of the bean plants increased with the increasing amounts of compost added to the soil, attributed to the phytonutritive capacity of compost. Biomass decreased with increasing As concentrations, however, the reduction in the biomass was significantly lower with the addition of compost, indicating that the As phytotoxicity was alleviated by the compost. For the same As concentration, the As content of the roots, shoots and beans decreased with increasing compost added compared to the Control. This is due to partial immobilization of the As by the organic functional groups on the compost, either directly or through cation bridging. Most of the As adsorbed by the bean plants accumulated in the roots, while a scant allocation of As occurred in the beans. Hence, the addition of compost to soils could be used as an effective means to limit As accumulation in crops from As-contaminated waters.

The competitive sorption among Cu, Pb and Cr in ternary system on Na-montmorillonite at pH 3.5, 4.5 and 5.5 and at different heavy metal concentrations, and the effect of varying concentrations of Al, Fe, Ca and Mg on the sorption of heavy metals were studied. Competitive sorption of Cu, Pb and Cr in ternary system on montmorillonite followed the sequence of Cr ≫ Cu > Pb. Moreover, the competition was weakened by the increase of pH while was intensified by the increase of heavy metal concentration. The sorption of heavy metal on montmorillonite was inhibited by the presence of Ca and Mg, while Al and Fe showed different patterns in affecting heavy metal sorption. Aluminum and Fe generally inhibited the sorption of heavy metal when the pH and/or concentration of major elements were relatively low. However, promoting effects on heavy metal sorption by Al and Fe were found at relatively high pH and/or great concentration of major elements. The inhibition of major elements on heavy metal sorption generally followed the order of Al > Fe > Ca ≥ Mg, while Fe was more efficient than Al in promoting the sorption of heavy metals. These findings are of fundamental significance for evaluating the mobility of heavy metals in polluted environments.

In soil environments, sorption/desorption reactions as well as chemical complexation with inorganic and organic ligands and redox reactions, both biotic and abiotic, are of great importance in controlling their bioavailability, leaching and toxicity. These reactions are affected by many factors such as pH, nature of the sorbents, presence and concentration of organic and inorganic ligands, including humic and fulvic acid, root exudates, microbial metabolites and nutrients. In this review, we highlight the impact of physical, chemical, and biological interfacial interactions on bioavailability and mobility of metals and metalloids in soil. Special attention is devoted to: i) the sorption/desorption processes of metals and metalloids on/from soil components and soils; ii) their precipitation and reduction-oxidation reactions in solution and onto surfaces of soil components; iii) their chemical speciation, fractionation and bioavailability.

The role of phosphorus (P) application and arbuscular mycorrhizal fungi (AMF) on growth, arsenic (As) and P accumulation in lettuce plants growing in an As-polluted soil (total As 250 mg kg−1), was investigated. In particular, it was tested whether application of a commercial inoculum (CI), with (+P at 90 kg P ha−1) and without (−P at 0 kg P ha−1) P fertilizer, supported greater plant growth and provided more P, enhancing As tolerance, than indigenous fungi alone. The influence of these treatments on As and P availability in the rhizosphere and bulk soils was also investigated. Greenhouse pot experiments were established where plants were grown with and without commercial inoculum (+CI, −CI) in unsterilized conditions. Inoculation with commercial inoculum and P application together considerably increased plant biomass, by enhancing host plant P nutrition and lowering shoot and root As concentrations compared to plants inoculated only with native AMF. In the rhizosphere of +CI+P plants there was P soil depletion compared to −CI+P. The results evidenced that, with P addition, inoculation with commercial inoculum alleviated the toxicity of excessive As by improving P nutrition without increasing As concentrations in the plant, emphasizing the role of beneficial microbes and P fertilizer to improve soil fertility in As-contaminated soil.

In this study we have examinated the results of two experiments on the uptake and distribution of arsenic (As) in roots, shoots, and grain of wheat grown in As-polluted soils and in an unpolluted soil irrigated with As-contaminated water in absence or presence of phosphorus (P) fertilization. Arsenic concentrations in wheat samples of the two experiments are higher than those in the plants grown on uncontaminated soil. In the experiments showed in this work, it is highlighted the role of P fertilization in preventing As uptake and translocation in wheat plants. These findings could have important implications to reduce the potential risk posed to human health by As entering the food-chain.

A study was conducted to determine the solid phase distribution of copper in representative soils of Italy with wide differences in the chemical and physicochemical properties. Sites selected varie...