Environmental assessment of phosphogypsum: A comprehensive geochemical modeling and leaching behavior study.

Understanding the variations in the geochemical composition of phosphogypsum (PG) destined for storage or valorization is crucial for assessing the safety and operational efficacy of waste management. The present study aimed to investigate the environmental behavior of PG using different leaching tests and to evaluate its geochemical behavior using geochemical modeling. Regarding the chemical characterization, the PG samples were predominantly composed of Ca (23.03-23.35 wt%), S (17.65-17.71 wt%), and Si (0.75-0.82 wt%). Mineralogically, the PG samples were primarily composed of gypsum (94.2-95.9 wt%) and quartz (1.67-1.76 wt%). Moreover, the automated mineralogy revealed the presence of apatite, fluorine and malladrite phases. The overall findings of the leaching tests showed that PG could be considered as non-hazardous material according to US Environmental Protection Agency limitations. However, a high leachability of elements at a L/S of 2 under acidic conditions ([Ca] = 166.52-199.87 mg/L, [S] = 207.9-233.59 mg/L, [F] = 248.62-286.65 mg/L) is observed. The weathering cell test revealed a considerable cumulative concentration over 90 days indicating potential adverse effects on the nearby environment (S: 8000 mg/kg, F: 3000 mg/kg, P: 700 mg/kg). Based on these results, it could be estimated that the surface storage of PG could have a serious impact on the environment. In this context, a simulation model was developed based on weathering cell results showed encouraging results for treating PG leachate using CaO before its disposal. Additionally, PHREEQC was used to analyze the speciation of major elements and calculate mineral phase saturation indices in PG leaching solutions. The findings revealed pH-dependent speciation for Ca, S, P, and F. The study identified gypsum, anhydrite, and bassanite as the key phases governing the dissolution of these elements.

Impact of sediment mobilization on trace elements release in Galician Rías (NW Iberian Peninsula): insights into aquaculture.

In the latest years, the concentration levels of certain metals and metalloids in the sediments of the Galician Rías have shown an increasing trend (e.g., As, Zn, Cu, Pb, Hg). These areas are also characterized by their richness in nutrients and their great aquaculture or mariculture activity, with the presence of more than 3500 mussel rafts in the Rías Baixas. The inner areas of the Galician Rías are subjected to activities that resuspend the sediment such as high levels of maritime traffic and dredging or cleaning operations. It is likely that a transfer of these elements to the water column happens during the resuspension of sediments caused by natural events or anthropogenic activities. In this study, selected samples of surface sediments of the Ría de Pontevedra (NW Spain) were subjected to a procedure of aerobic oxidation to determine the concentration of some elements (Fe, Mn, Cu, Cr, Pb, Hg, and Zn) released from the sediment to the aqueous phase. The experiment was carried out within 5 days. Measurements of pH and total concentration were taken both in water and sediment samples. Furthermore, speciation of trace elements was carried out in the sediment samples. Trace element concentrations were lower in the sediments during aerobic oxidation, being released to the aqueous phase. From an environmental point of view, Cu was the only trace element released in quantities that may be toxic for the organisms in the area. This problem of sediment oxidation related to dredging activities or natural storm conditions should be considered in environmental impact studies and transferred to stakeholders.

Adverse health and environmental outcomes of sewage treatment plant on surrounding groundwater with emphasis on some mitigation recommendations.

Water quality deterioration hinders economic and social development in developing countries that are facing freshwater security and shortages. Based on the collection of 29 water samples, this study focused on the relationship between sewage treatment plant and groundwater system surrounding it using multidisciplinary approach that combines the characterization of groundwater system and its connection with surrounding canal and drains, using chemical and isotopic characterization revealing that there is a direct relation between the surface water system and surrounding groundwater system. About 58% of the groundwater samples and all surface water samples in the investigated area are threatened by high concentrations of trace elements. The multivariate statistical analysis elucidates that anthropogenic effect and fertilizers sewage contamination are the main causes of groundwater pollution. Nearly, 31% and 11.5% of groundwater samples were posing oral chronic non-carcinogenic health risk and dermal chronic risk for adult, respectively, while all surface water samples were posing oral chronic non-carcinogenic health risk, with no dermal hazard. The uncharged species of Fe and Al are expected to be more mobile in groundwater because they would not be attracted to the surface charge of minerals. Inorganic ligands (HCO3-, SO42-, Cl-, and NO3-) act as nucleation centers that were linked with those trace elements creating new species with higher solubility degree in water that are transported away randomly for long distances in the water path.

Simultaneous Quantification and Speciation of Trace Metals in Paired Serum and CSF Samples by Size Exclusion Chromatography-Inductively Coupled Plasma-Dynamic Reaction Cell-Mass Spectrometry (SEC-DRC-ICP-MS).

BACKGROUND: Transition metals play a crucial role in brain metabolism: since they exist in different oxidation states they are involved in ROS generation, but they are also co-factors of enzymes in cellular energy metabolism or oxidative defense. METHODS: Paired serum and cerebrospinal fluid (CSF) samples were analyzed for iron, zinc, copper and manganese as well as for speciation using SEC-ICP-DRC-MS. Brain extracts from Mn-exposed rats were additionally analyzed with SEC-ICP-DRC-MS. RESULTS: The concentration patterns of transition metal size fractions were correlated between serum and CSF: Total element concentrations were significantly lower in CSF. Fe-ferritin was decreased in CSF whereas a LMW Fe fraction was relatively increased. The 400-600 kDa Zn fraction and the Cu-ceruloplasmin fraction were decreased in CSF, by contrast the 40-80 kDa fraction, containing Cu- and Zn-albumin, relatively increased. For manganese, the α-2-macroglobulin fraction showed significantly lower concentration in CSF, whereas the citrate Mn fraction was enriched. Results from the rat brain extracts supported the findings from human paired serum and CSF samples. CONCLUSIONS: Transition metals are strictly controlled at neural barriers (NB) of neurologic healthy patients. High molecular weight species are down-concentrated along NB, however, the Mn-citrate fraction seems to be less controlled, which may be problematic under environmental load.

Investigation of total zinc contents and zinc-protein profile in medicinal plants traditionally used for diabetes treatment.

This study aims at the assessment of total zinc contents, water zinc extract contents and zinc-protein profile in medicinal plants traditionally used for diabetes treatment. While zinc-protein profile was screened in plant samples using the online coupling of size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS), total zinc contents and zinc water extract contents were determined using inductively coupled plasma-optical emission spectrometry (ICP-OES). The analysis of two certified reference materials with similar matrix for total zinc content revealed recovery values of 97.1% and 100.5% while the average of recovery of the summed Zn concentrations from protein fractions compared to total Zn was 103.0 ± 4.8%. Based on the FAO/WHO classification, Sesamum indicum, Nigella sativa, Trigonella Foenum-graecum and Pennisetum glaucum are classified as highest Zn-content. For protein profile, zinc was quantified in 330-430 and 50-60 kDa fractions of all examined plants while no contents were quantified in the inorganic fraction 0.05-0.4 kDa of all plant species. Also, only three plant species recorded Zn contents in the phytate fraction (0.9-1.5 kDa fraction). The fruits of the Momordica Charantia and the Citrullus colocynthis were with the highest extractable zinc concentration; 13.55 ± 0.45 and 10.08 ± 0.63 mg/kg, respectively. The highest Zinc capturing capacity was reported for the 50-60 and 70-87 KDa protein fractions.

Zinc isotope fractionation during grain filling of wheat and a comparison of zinc and cadmium isotope ratios in identical soil-plant systems.

Remobilization of zinc (Zn) from shoot to grain contributes significantly to Zn grain concentrations and thereby to food quality. On the other hand, strong accumulation of cadmium (Cd) in grain is detrimental for food quality. Zinc concentrations and isotope ratios were measured in wheat shoots (Triticum aestivum) at different growth stages to elucidate Zn pathways and processes in the shoot during grain filling. Zinc mass significantly decreased while heavy Zn isotopes accumulated in straw during grain filling (Δ66 Znfull maturity-flowering  = 0.21-0.31‰). Three quarters of the Zn mass in the shoot moved to the grains, which were enriched in light Zn isotopes relative to the straw (Δ66 Zngrain-straw -0.21 to -0.31‰). Light Zn isotopes accumulated in phloem sinks while heavy isotopes were retained in phloem sources likely because of apoplastic retention and compartmentalization. Unlike for Zn, an accumulation of heavy Cd isotopes in grains has previously been shown. The opposing isotope fractionation of Zn and Cd might be caused by distinct affinities of Zn and Cd to oxygen, nitrogen, and sulfur ligands. Thus, combined Zn and Cd isotope analysis provides a novel tool to study biochemical processes that separate these elements in plants.

Nutrition potential of biogas residues as organic fertilizer regarding the speciation and leachability of inorganic metal elements.

Biogas residues (BRs) are prospective organic fertilizer sources for agricultural cultivation. Besides N and P, however, other inorganic metal elements, such as K, Fe, Cu, Zn and so on, also affect the nutritional level of BRs significantly. In this study, a sequential extraction procedure (SEP) combined with a toxicity characteristic leaching procedure (TCLP) was conducted to investigate the speciation and leachability of metal components in BRs. The results showed that element K was the most effective nutrient component due to its largest available fraction and highest mobility factor (MF) of 78.4, whereas phytotoxic Al was the most stable and inert element in terms of its 96.68% residual fraction. Ca and Mg could be viewed as potential nutrient sources because their MFs exceeded 60. TCLP results revealed that these BRs could be classed as non-toxic organic waste but Cu and Zn should be paid more attention in that their total contents were beyond the permissible values. Meanwhile, more concerns should be given to Ni and Pb due to their large TCLP extractable fraction. In conclusion, these BRs can be used as a prospective nutrient pool for agricultural cultivation. SEP combined with TCLP can be effectively applied for assessing the nutrient level of the BRs as organic fertilizer for agricultural use.

Arsenic speciation and arsenic feed-to-fish transfer in Atlantic salmon fed marine low trophic feeds based blue mussel and kelp.

BACKGROUND: Aquaculture aims to reduce the environmental and climate footprints of feed production. Consequently, low trophic marine (LTM) resources such as blue mussels and kelp are potential candidates to be used as ingredients in salmon feed. It is relevant to study potential undesirables associated with their use, as well as assessing food safety by investigating their transfer from feed-to-fish. The marine biota is well known to contain relatively high levels of arsenic (As), which may be present in different organic forms depending on marine biota type and trophic position. Thus, it is important to not only obtain data on the concentrations of As, but also on the As species present in the raw materials, feed and farmed salmon when being fed novel LTM feed resources. METHODS: Atlantic salmon were fed experimental diets for 70 days. A total of nine diets were prepared: four diets containing up to 4 % fermented kelp, three diets containing up to 11 % blue mussel silage, and one diet containing 12 % blue mussel meal, in addition to a standard reference diet containing 25 % fish meal. Concentrations of As and As species in feeds, faeces, liver and fillet of Atlantic salmon were determined by inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography coupled to ICP-MS (HPLC-ICP-MS), respectively. RESULTS: The use of kelp or blue mussel-based feed ingredients increased the concentration of total As, but maximum level as defined in Directive 2002/32 EC and amendments was not exceeded. The concentrations found in the experimental feeds ranged from 3.4 mg kg-1 to 4.6 mg kg-1 ww. Arsenic speciation in the feed varied based on the ingredient, with arsenobetaine dominating in all feed samples (36-60 % of the total As), while arsenosugars (5.2-8.9 % of the total As) were abundant in kelp-included feed. The intestinal uptake of total As ranged from 67 % to 83 %, but retention in fillet only ranged from 2 % to 22 % and in liver from 0.3 % to 0.6 %, depending on the marine source used. Fish fed feeds containing blue mussel showed higher intestinal uptake of total As when compared with fish fed feeds containing fermented kelp. Fish fed fermented kelp-based feeds had higher retained concentrations of total As when comparing with fish fed feeds containing blue mussel. Despite relatively high intestinal uptake of total As, inorganic and organic As, the retained concentrations of As did not reflect the same trend. CONCLUSION: Although the use of LTM feed ingredients increased the level of total As in this feeds, salmon reared on these diets did not show increased total As levels. The well-known toxic inorganic As forms were not detected in salmon muscle reared on LTM diets, and the non-toxic organic AsB was the dominant As species that was retained in salmon muscle, while the organic AsSug forms were not. This study shows that speciation analysis of the LTM resources provides valuable information of the feed-to-fish transfer of As, needed to assess the food safety of farmed Atlantic salmon reared on novel low trophic feeds.

Arsenic speciation analysis in honey bees for environmental monitoring.

Arsenic can be toxic to living organisms, depending not only on the concentration, but also its chemical form. The aim of this study was to determine arsenic concentrations and perform arsenic speciation analysis for the first time in honeybees, to evaluate their potential as biomonitors. Highest arsenic concentrations were determined in the vicinity of coal fired thermal power plants (367 µg kg-1), followed by an urban region (213 µg kg-1), with much lower concentrations in an industrial city (28.8 µg kg-1) and rural areas (41 µg kg-1). Until now, honey bees have never been used to study different arsenic species in the environment. For this reason, four extraction procedures were tested: water, hot water at 90 °C, 20% methanol, and 1% formic acid. Water at 90 °C was able to extract more than 90% of the total arsenic from honey bee samples. Inorganic arsenic (the sum of arsenite and arsenate) accounted for 95% of arsenic species in bees from three locations, except the industrial city, where it represented only 80% of arsenic species, while 15% was present as DMA.

Arsenic species in mesopelagic organisms and their fate during aquafeed processing.

A responsible harvest of mesopelagic species as aquafeed ingredients has the potential to address the United Nations Sustainable Development Goal 14, which calls for sustainable use of marine resources. Prior to utilization, the levels of undesirable substances need to be examined, and earlier studies on mesopelagic species have reported on total arsenic (As) content. However, the total As content does not give a complete basis for risk assessment since As can occur in different chemical species with varying toxicity. In this work, As speciation was conducted in single-species samples of the five most abundant mesopelagic organisms in Norwegian fjords. In addition, As species were studied in mesopelagic mixed biomass and in the resulting oil and meal feed ingredients after lab-scale feed processing. Water-soluble As species were determined based on ion-exchange high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). This was supplemented by extracting arsenolipids (AsLipids) and determining total As in this fraction. The non-toxic arsenobetaine (AB) was the dominant form in mesopelagic crustaceans and fish species, accounting for approximately 70% and 50% of total As, respectively. Other water-soluble species were present in minor fractions, including carcinogenic inorganic As, which, in most samples, was below limit of quantification. The fish species had a higher proportion of AsLipids, approximately 35% of total As, compared to crustaceans which contained 20% on average. The feed processing simulation revealed generally low levels of water-soluble As species besides AB, but considerable fractions of potentially toxic AsLipids were found in the biomass, and transferred to the mesopelagic meal and oil. This study is the first to report occurrence data of at least 12 As species in mesopelagic organisms, thereby providing valuable information for future risk assessments on the feasibility of harnessing mesopelagic biomass as feed ingredients.