Huelva is a highly industrialized city in SW Spain hosting, among others, a Cu smelter, a phosphate fertilizer plant, a power plant, and oil refineries. This study aims to evaluate metal concentrations in lichens as bioindicators of atmospheric pollution in the impacted urban areas. Xanthoria parietina species from Huelva and nearby villages, as well as reference samples from remote, non-contaminated urban areas, were analyzed for trace elements (V, Cr, Mn, Co, Ni, Cu, Zn, Sr, As, Cd, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Er, Tm, Yb, Lu, Pb, Th, U) using Inductively Coupled Plasma-Mass Spectrometry; and for major elements (Ca, K, Mg, P, and S) by Inductively Coupled Plasma-Optical Emission Spectrometry after acid digestion.The metal composition of X. parietina exhibits spatial distribution patterns with extremely elevated concentrations (Co, Ni, Cu, Zn, As, Cd, Sb, Ba, Pb, U, and S) in the surroundings of the industrial estates to <1 km distance. Mean concentrations were significantly lower in the urban areas >1 km from the pollution sources. However, air pollution persists in the urban areas up to 4 km away, as the mean concentrations of Cu, Zn, As, Cd, Sb and S remained considerably elevated in comparison to the reference samples. Though rigorous source apportionment analysis was not the aim of this study, a good positive correlation of our results with metal abundances in ambient particulate matter and in pollution sources points to the Cu smelter as the main source of pollution. Hence, the severe air pollution affecting Huelva and nearby urban areas may be considered a serious health risk to local residents.

A biofilm reactor was designed with flat ceramic substrates to remove Co(II), Ni(II) and Zn(II) from industrial wastewater. The ceramics were made of clay and nano-rubber with high mechanical resistance. The surface of the ceramic substrate was modified with neutral fiber and nano-hydroxyapatite. A uniform and stable biofilm mass of 320 g with 2 mm of thickness was produced on the modified ceramic after 3 d. The micro-organisms were identified in the biofilm by polymerase chain reaction (PCR) method. Functional groups of biofilms were identified with a Fourier transform infrared spectrometer (FT-IR). Experiments were designed by central composite design (CCD) using the responsive surface method (RSM). The biosorption process was optimized at pH = 5.8, temperature = 22 °C, feed flux of heavy metal wastewater = 225 ml, substrate flow = 30 ml, and retention time = 7.825 h. The kinetic data was analyzed by pseudo first-order and pseudo second-order kinetic models. Isotherm models and thermodynamic parameters were applied to describe the biosorption equilibrium data of the metal ions on the biofilm-ceramic. The maximum biosorption efficiency and capacity of heavy metal ions were about 72% and 57.21 mg, respectively.

Enhancing metals phytoextraction using gentile mobilizing agents might be an appropriate approach to increase the phytoextraction efficiency and to shorten the phytoremediation duration. The effect of sulfur-impregnated organoclay (SIOC) on the redistribution of potentially toxic elements (PTEs) among their geochemical fractions in soils and their plant uptake has not yet been studied. Therefore, our aim is to investigate the role of different SIOC application doses (1%, 3% and 5%) on operationally defined geochemical fractions (soluble + exchangeable; bound to carbonate; manganese oxide; organic matter; sulfide; poorly- and well-crystalline Fe oxide; and residual fraction) of Cd, Cr, Cu, Ni, Pb, and Zn, and their accumulation by pea (Pisum sativum) and corn (Zea mays) in a greenhouse pot experiment using a polluted floodplain soil. The SIOC caused a significant decrease in soil pH, and an increase in organic carbon and total sulfur content in the soil. The addition of SIOC increased significantly the soluble + exchangeable fraction and bioavailability of the metals. The SIOC leads to a transformation of the residual, organic, and Fe-Mn oxide fractions of Cd, Cu, Ni, and Zn to the soluble + exchangeable fraction. The SIOC addition increased the potential mobile (non-residual) fraction of Cr and Pb. The SIOC increased the sulfide fraction of Cr, Ni, and Zn, while it decreased the same fraction for Cd, Cu, and Pb. The effect of SIOC on the redistribution of metal fractions increased with enhancing application dosages. Pea accumulated more metals than corn with greater accumulation in the roots than shoots. Application of the higher dose of SIOC promoted the metals accumulation by roots and their translocation to shoots of pea and corn. Our results suggest the potential suitability of SIOC for enhancing the phytomanagement of PTEs polluted soils and reducing the environmental risk of these pollutants.

Although, health and environmental hazards of Ni are ironclad; however, that of Nickle oxide nanoparticles (NiO-NPs) are still obscure. Therefore, impact of NiO-NPs exposure (0, 5, 50, 200, 500 and 1000 mg kg⁻¹ soil) on the earthworm (Eisenia fetida) survival (at 28th day), reproduction (at 56th day), histopathology, ultrastructures, antioxidant enzymes and oxidative DNA damage was appraised in full life cycle study. Lower concentrations of NiO-NPs (5, 50 and 200) did not influence the survival, reproduction and growth rate of adult worms significantly. However, reproduction reduced by 40–50% with 500 and 1000 mg kg⁻¹ exposure, which also induced oxidative stress leading to DNA damage in earthworms. Ultrastructural observation and histology of earthworms exposed to higher NiO-NPs concentrations revealed abnormalities in epithelium layer, microvilli and mitochondria with underlying pathologies of epidermis and muscles, as well as adverse effects on the gut barrier. To the best of our knowledge, this is the first study unveiling the adverse effects of NiO-NPs on a soil invertebrate (Eisenia fetida). Our findings clue towards looking extensively into the risks of NiO-NPs on soil organisms bearing agricultural and environmental significance.

In modern society, the intense vehicle traffic and the lack of effective mitigating strategies may adversely impact freshwater systems. Road-deposited sediments (RDS) accumulate a variety of toxic substances which are transported into nature during hydrologic events, mainly affecting water bodies through stormwater runoff. The aim of this study was to evaluate the RDS metal enrichment ratio between the end of wet season and the middle of the dry season for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in samples from Natal, Brazil. Twenty RDS, drainage system and river sediment samples were collected in the wet and dry seasons using a stainless-steel pan, brush and spatula. In the laboratory, the samples were submitted to acid digestion and heavy metal concentrations were measured by atomic absorption spectrometry (AAS). A consistent RDS enrichment by heavy metals in dry season samples was followed by an increase in the finest particle size fraction (D < 63 μm). Maximum concentrations were 5, ND, 108, 23810, 83, ND, 77 and 150 mg kg⁻¹ for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn, respectively. The RDS enrichment ratio was Cr(1.3 ×), Cu(2.6 ×), Fe(3.3 ×), Mn(1.5 ×), Pb(1.5 ×) and Zn(2.1 ×). The Geo-accumulation Index values showed that RDS were moderately polluted for Cu and slighted polluted for Zn and Pb. Principal Component Analysis (PCA) showed that the accumulation of toxic heavy metals decreased according to water flow.

Waste water of the Kettara village, as well as the abandoned tailings, constitute a potential environmental issue with direct consequences on air, soil, water resources qualities and, on human health. In this paper, experimental investigations examine the environmental impact which is induced by the wastewater, mine tailings and the lithological factors of rocks. This multidisciplinary research allows to i) understand the transfer of the Metallic Trace Elements (selenium, arsenic, nickel and zinc) and sulfate ions in the fractured shales media, ii) to assess the water potability by using the microbiological analysis. The microbiological results reveal the domestic impact by the presence of several kinds of bacteria in the groundwater resources: E. coli, Fecal coliforms, Total coliforms, Enterococci, Mesophilic Aerobic Flora, Sulphite-reducing bacteria and Salmonella.Selenium, arsenic and the bacteriological contamination of the groundwater could be explained by five kinds of factors: i) the geological formations and the nature of the hydrogeological system (unconfined layer), ii) the groundwater flow, the hydraulic relation between the hydrogeological wells and, the fractures network in the shale aquifer. The piezometric map allows to highlight the groundwater flow from the North-East to North-West and to the South-West, the drainage axis towards the P21 well and the presence of the dividing axis in the contaminated zone by the arsenic, iii) the absence of the unhealthy habitats with permeable traditional septic tanks in the village; iv) the transfer of the spreading animal excrements from the soil to groundwater and, v) the migration of the wastewater towards downstream of the groundwater flow. The presence of the reed beds could explain the reduction of bacteria in the hydrogeological wells of the study area.

Metal flux measurements inform the mobility, potential bioavailability and risk of toxicity for metals in contaminated sediments and therefore is an important approach for sediment quality assessment. The binding and release of metals that contribute to the net flux is strongly influenced by the presence and behaviors of benthic organisms. Here we studied the effects of bioturbation on the mobility and efflux of metals from multi-metal contaminated sediments that inhabited by oligochaete worms or both worms and bivalves. Presence of bivalves enhanced the release of Mn, Co, Ni and Zn but not for copper and chromium, which is likely due to the high affinities of copper and chromium for the solid phase. Metals in the overlying water were primarily associated with fractions smaller than 10 kDa, and the fractionation of all metals were not affected by the presence of the bivalve. Metal fluxes attributed to different processes were also distinguished, and the bioturbation induced effluxes were substantially higher than the diffusive effluxes. Temporal variabilities in the total net effluxes of Mn, Co, Ni and Zn were also observed and were attributed to the biological activities of the bivalves. Overall, the present study demonstrated that the response of different metals to the same bioturbation behavior was different, resulting in distinct mobility and fate of the metal contaminants.

Nickel nanoparticles (NiNPs) have an estimated production of ca. 20 tons per year in the US. Nickel has been risk-assessed for long in Europe, but not NiNPs, hence the concern for the environment. In the present study, we focused on investigating the mechanisms of toxicity of NiNPs and the comparison to NiNO3. The high-throughput microarray for the soil ecotox model Enchytraeus crypticus (Oligochaeta) was used. To anchor gene to phenotype effect level, organisms were exposed to reproduction effect concentrations EC20 and EC50, for 3 and 7 days. Results showed commonly affected pathways between NiNPs and NiNO3, including increase in proteolysis, apoptosis and inflammatory response, and interference with the nervous system. Mechanisms unique to NiNO3 were also observed (e.g. glutathione synthesis). No specific mechanisms for NiNPs were found, which could indicate that longer exposure period (>7 days) is required to capture the peak response to NiNPs. A mechanisms scheme is assembled, showing both common and unique mechanisms to NiNO3 and NiNPs, providing an important framework for further, more targeted, studies.

Crested ibis (Nipponia nippon), one of the rarest birds in the world, was almost extinct in the historically widespread areas partly due to the environmental pollution. Therefore, non-invasive indicators of feather, eggshell, and excrement were used to investigate the exposure of this endangered bird to eleven trace elements in this study. The results indicated that crested ibises under in situ and ex situ conservations were diversely exposed to trace elements, with higher exposure levels of As, Cd, and Mn in the wild, but higher exposure levels of Hg, Se, and Zn in the captive breeding center. In addition, concentrations of As, Co, Cr, and Ni were significantly greater in the sediments of three types of foraging habitats for wild crested ibis, but concentration of Se was greater in the soil of captive cages. Feather and eggshell of crested ibis exhibited a very consistent indication for most of the trace elements, and concentrations of almost all of the elements in the excrements were very consistent with the results in the environmental samples (sediments or soils). Concentrations of As, Hg, Mn, and Zn in feathers, and Mn and Zn in eggshells of wild and captive crested ibis were greater than those in other similar species. Moreover, As, Cd, Cu, and Mn concentrations in excrement of wild crested ibises were greater than that in captive individuals and other species, but Se and Zn concentrations in excrement of captive crested ibises were greater than that of the wild and other species. The present study provided evidence that both of the wild and captive crested ibis were exposed to trace elements, which may be harmful to their health.

Agricultural soil is one of the main sink for both heavy metals and nanomaterials (NMs). Whether NMs can impact heavy metals uptake or bioaccumulation in plants is unknown. Here, cucumber plants were cultivated in a multi-heavy metals contaminated soil amended with four types of NMs (SiO2, TiO2, ZnS and MoS2) separately for four weeks. Physiological and biochemical parameters were determined to investigate the impact of NMs on plant growth. Inductively coupled plasma mass spectrometry was employed to determine the metal content in plants. Results showed that none of the tested NMs impacted plants biomass, but all the NMs showed different degrees of reduction in heavy metals bioaccumulation in plant roots, stems and leaves. However, four NMs showed different degrees of reduction in macro and micro nutrients uptake. MoS2 decreased the bioaccumulation of heavy metals (As, Cd, Cr, Cu, Ni, Al, Ti and Pb) for 36.4–60.6% and nutrients (Mg, Fe, K, Si and Mn) for 40.1%–50.1% in roots. Exposure to MoS2 NMs also significantly increased 23.4% of Si in leaves, 205.6% and 83.9% of Mo in roots and stems, respectively. In general, the results of this study showed promising potential for NMs to reduce uptake of heavy metals in crop plants, especially MoS2 NMs. However, the negative impacts of perturbing nutrients uptake should be paid attention as well.