Cacao from South America is especially used to produce premium quality chocolate. Although the European Food Safety Authority has not established a limit for cadmium (Cd) in chocolate raw material, recent studies demonstrate that Cd concentrations in cacao beans can reach levels higher than the legal limits for dark chocolate (0.8 mg kg−1, effective January 1st, 2019). Despite the fact that the presence of Cd in agricultural soils is related to contamination by fertilizers, other potential sources must be considered in Ecuador. This field study was conducted to investigate Cd content in soils and cacao cultivated on Ecuadorian farms in areas impacted by oil activities. Soils, cacao leaves, and pod husks were collected from 31 farms in the northern Amazon and Pacific coastal regions exposed to oil production and refining and compared to two control areas. Human gastric bioaccessibility was determined in raw cacao beans and cacao liquor samples in order to assess potential health risks involved. Our results show that topsoils (0–20 cm) have higher Cd concentrations than deeper layers, exceeding the Ecuadorian legislation limit in 39% of the sampling sites. Cacao leaves accumulate more Cd than pod husks or beans but, nevertheless, 50% of the sampled beans have Cd contents above 0.8 mg kg−1. Root-to-cacao transfer seems to be the main pathway of Cd uptake, which is not only regulated by physico-chemical soil properties but also agricultural practices. Additionally, natural Cd enrichment by volcanic inputs must not be neglected. Finally, Cd in cacao trees cannot be considered as a tracer of oil activities. Assuming that total Cd content and its bioaccessible fraction (up to 90%) in cacao beans and liquor is directly linked to those in chocolate, the health risk associated with Cd exposure varies from low to moderate.

Rice is one of the major pathways of arsenic (As) exposure in human food chain, threatening over half of the global population. Greenhouse pot experiments were conducted to examine the effects of Si application on iron (Fe) plaque formation, As uptake and rice grain As speciation in indica and hybrid rice genotypes with different radial oxygen loss (ROL) ability. The results demonstrated that Si significantly increased root and grain biomass. Indica genotypes with higher ROL induced greater Fe plaque formation, compared to hybrid genotypes and sequestered more As in Fe plaque. Silicon applications significantly increased Fe concentrations in iron plaque of different genotypes, but it decreased As concentrations in the roots, straws and husks by 28–35%, 15–35% and 32–57% respectively. In addition, it significantly reduced DMA accumulation in rice grains but not inorganic As accumulation. Rice of indica genotypes with higher ROL accumulated lower concentrations of inorganic As in grains than hybrid genotypes with lower ROL.

Bush bean (Phaseolus vulgaris) was exposed to atmospheric deposition of As, Cd and Pb in a polluted and a reference area. The atmospheric deposition of these elements was significantly related to the concentrations in leaves, stems and pods at green harvest. Surprisingly there was also a clear relation for As and Pb in the seeds at dry harvest, even though these seeds were covered by the husks. Root uptake of accumulated atmospheric deposits was not likely in such a short term experiment, as confirmed by the fact that soil pore water analysis did not reveal significant differences in trace element concentrations in the different exposure areas. For biomonitoring purposes, the leaves of bush bean are the most suitable, but also washed or unwashed pods can be used. This means that the obtained relationships are suitable to estimate the transfer of airborne trace elements in the food chain via bush bean.

The natural occurrence of arsenic (As) in groundwater & soils and its bioaccumulation in rice grains is a major health concern worldwide. To combat the problem, best combination of irrigation management and suitable rice variety altering As content in grains must be ensured. With this aim, a field trial was conducted with two rice varieties and water management including alternate wetting and drying (AWD) and continuous flooding (CF) irrigation regimes with As contaminated groundwater (AsW) and temporarily stored groundwater (TSG) and river water for only CF (as control). Results revealed that As content in different portions of paddy plant was significantly different (P < 0.001) with irrigation practices and rice varieties. AWD irrigation with TSG accumulated lower As in rice grains compared with CF-AsW for both varieties. Data showed that AWD-TSG practice led to 61.37% and 60.34% grain As reduction for BRRI dhan28 and BRRI dhan29, respectively, compared with CF-AsW. For Principle Component Analysis (PCA), first principle component (PC1) explained 91.7% of the variability and irrigation water As, soil total and available As, straw As, root As and husk As were the dominating parameters. With significant (P < 0.05) variation in yields between the genotypes, AWD increased grain yield by 29.25% in BRRI dhan29 Compared with CF. However, translocation factor (TF) and bioconcentration factor (BCF) for both varieties were less than one for all the treatments. The addition of this study to our knowledge base is that, AWD-TSG with BRRI dhan29 can be an As–safe practice without compromising yields.

Metabolism of sulfur (S) is suggested to be an important factor for the homeostasis and detoxification of Cu in plants. We investigated the effects of S fertilizers (S0, Na2SO4) on Cu translocation and biotransformation in rice plants by using multiple synchrotron-based techniques. Fertilization of S increased the biomass and yield of rice plants, as well as the translocation factor of Cu from root to shoot and shoot to grain, resulting in enhanced Cu in grain. Sulfur K-edge X-ray near edge structure (XANES) analysis showed that fertilization of S increased the concentration of glutathione in different rice tissues, especially in rice stem and leaf. Copper K-edge XANES results indicated that a much higher proportion of Cu (I) species existed in rice grain than husk and leaf, which was further confirmed by soft X-ray scanning transmission microscopy results. Sulfur increased the proportion of Cu (I) species in rice grain, husk and leaf, suggesting the inducing of Cu (II) reduction in rice tissues by S fertilization. These results suggested that fertilization of S in paddy soils increased the accumulation of Cu in rice grain, possibly due to the reduction of Cu (II) to Cu (I) by enhancing glutathione synthesis and increasing the translocation of Cu from shoot to grain.

Rice is a staple food and major source of nutrients, but it also bioaccumulates toxic elements. In this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to determine tissue-level trace metal spatial distribution in rice (Oryza sativa) seeds from the active Xikuangshan Sb mine area in China. Whole grain quantified elemental bioimages showed the highest concentration of Zn (1755 mg/kg) in the embryo andmicro zones of elevated Sb, As, Pb, Cd as high as 280, 57, 31 and 830 mg/kg, respectively on the husk/bran/endosperm tissues. Bioimages suggest that both Sb and Cd may be competing with Zn for binding sites. Both Sb(III) and Sb(V) species were detected in seeds from upstream and downstream fields indicating the presence of toxic Sb(III). Brown rice is a good source of Zn, but white rice is a safer option if rice is grown in a polluted area.

The consumption of paddy rice (Oryza sativa L.) is a major inorganic arsenic exposure pathway in S.E. Asia. A multi-location survey was undertaken in Guangdong Province, South China to assess arsenic accumulation and speciation in 2 rice cultivars, one an Indica and the other a hybrid Indica. The results showed that arsenic concentrations in rice tissue increased in the order grain < husk < straw < root. Rice grain arsenic content of 2 rice cultivars was significant different and correlated with phosphorus concentration and molar ratio of P/As in shoot, being higher for the Indica cultivar than for the hybrid Indica, which suggests altering shoot phosphorus status as a promising route for breeding rice cultivars with reduced grain arsenic. Speciation of grain arsenic, performed using HPLC-ICP-MS, identified inorganic arsenic as the dominant arsenic species present in the rice grain.

Despite arsenic (As) bioavailability being highly correlated with water status and the presence of iron (Fe) minerals, limited information is currently available on how externally applied Fe nanomaterials in soil-rice systems affect As oxidation and stabilization during flooding and draining events. Herein, the stabilization of As in a paddy soil by a phytosynthesized iron oxide nanomaterials (PION) and the related mechanism was investigated using a combination of chemical extraction and functional microbe analysis in soil at both flooding (60 d) and draining (120 d) stages. The application of PION decreased both specifically bound and non-specifically bound As. The As content in rice root, stem, husk and grain was reduced by 78.5, 17.3, 8.4 and 34.4%, respectively, whereas As(III) and As(V) in root declined by 96.9 and 33.3% for the 1% PION treatment after 120 d. Furthermore, the 1% PION treatment decreased the ratio of As(III)/As(V) in the rhizosphere soil, root and stem. Although PION had no significant effect on the overall Shannon index, the distribution of some specific functional microbes changed dramatically. While no As(III) oxidation bacteria were found at 60 d in any treatments, PION treatment increased As(III) oxidation bacteria by 3–9 fold after 120 d cultivation. Structural equation model analysis revealed that the ratio of Fe(III)/Fe(II) affected As stabilization directly at the flooding stage, whereas nitrate reduction and As(III) oxidation microbial groups played a significant role in the stabilization of As at the draining stage. These results highlight that PION exhibits a robust ability to reduce As availability to rice, with chemical oxidation, reduction inhibition and adsorption dominating at the flooding stage, while microbial oxidation, adsorption and coprecipitation dominant during draining.

Heavy metal pollution is becoming recurrent and threatens biota biosafety in many agricultural fields. Diverse solutions explore the application of amendments to enable remediation. Sulfur represents a nonmetallic chemical element that actively affects heavy metals phytoextraction, and promotes and alternatively mitigates soil functions. In this study, we conduct a meta-analysis to synthesize the current knowledge on the influence of sulfur amendments on plants heavy metals uptake from contaminated soil media. Random-effects model was used to summarize effect sizes from 524 data points extracted from 30 peer reviewed studies. The phytoextraction of cadmium, chromium and nickel were 1.6-, 3.3-, and 12.6-fold, respectively, higher when sulfur amendment was applied; while copper uptake was 0.3-fold lower. Irrespective of the sulfur type, heavy metal extraction increased with the raising sulfur stress. Individual organs showed significant differences of heavy metal uptake between sulfur applied and non-sulfur treatments, and combined organs did not. The heavy metals uptake in leaves and roots were higher in sulfur applied than non-sulfur applied treatments, while those in grain, husk, and stalks were lower. The heavy metals phytoextraction (response ratio) followed the order roots > leaves > stalk > grain > husk. Moreover, heavy metals uptake was 2-fold higher in the sulfur applied than the non-sulfur treatments under ideal (5.5–8) and alkaline conditions (8–14), and 0.2-fold lower under acidic pH (1–5.5). Cadmium, manganese and nickel, and chromium were the most extracted under sulfur application by Vicia sp., Sorghum sp. and Brassica sp., respectively; while chromium, manganese, and iron were the most uptake without sulfur amendments by Oryza sp., Zea sp. and Sorghum sp., respectively. Our study highlights that the influence of sulfur on heavy metal phytoextraction depends on the single or combined effects of sulfur stress intensity, sulfur compounds, plant organ, plant type, and soil pH condition.

The research was conducted to investigate the accumulation, distribution and availability of Cd in paddy soil and their relation to Cd in rice plants under 30-year fertilization regimes. Six treatments were involved in the study: control without fertilization (CK), chemical fertilizer (NPK), high nitrogen chemical fertilizer (HN), rice straw incorporation (ST), low and high dosage of manure fertilizer (LM and HM). Total and DTPA extractable concentration of Cd (T-Cd and DTPA-Cd) in bulk soils (20 cm topsoil), profiles (0–60 cm) and aggregates (>2, 1–2, 0.5–1, 0.25–0.5, 0.053–0.25 and < 0.053 mm) were investigated. The Cd concentration in relevant rice plant (roots, stems, leaves, husks and grains) were also analyzed. Manure fertilizers caused T-Cd accumulation in bulk soil with a significant increase of 36.2% in LM and 81.2% in HM. Similar impacts of manure fertilizers were observed in DTPA-Cd in the bulk soil. Further, the HM generated a further accumulation in deeper soil layers, presenting a remarkable increase of T-Cd (28.3%–225%) in 10–40 cm and DTPA-Cd (116%–158%) in 10–30 cm profiles. Moreover, the continuous application of manure fertilizers enhanced the availability of Cd in all aggregate size classes with an increase of 17.3%–87.8% in DTPA-Cd. Organic fertilizers (LM, HM and ST) heightened the content of Cd (38.0%–152%) in all parts of rice plant. The accumulation of Cd in rice plants was directly affected by fertilization regimes and Cd availability in the 10–20 cm soil layers and 0.25–0.5 mm aggregates. In conclusion, long-term application of manures resulted in increasing availability of Cd in aggregates and in topsoil and subsoil layers, which accordingly enhanced the accumulation of Cd in rice plants.