International audience | The abiotic transformations of quinolones and tetracyclines facilitated by redox-active minerals has been studied extensively, however limited information is available regarding the antimicrobial activity and toxicity of their resultant transformation products. In this study, we first investigated the mechanisms underlying the transformation of two commonly used antibiotics, ciprofloxacin (CIP) and tetracycline (TC), by the ubiquitous redox soil mineral, birnessite (MnO2). Subsequently, we evaluated the impact of these transformation products on both the growth and activity of the environmental denitrifier Pseudomonas veronii. Following the reaction with birnessite, four transformation products for CIP and five for TC were identified. Remarkably, the antibacterial activity of both CIP and TC was lost upon the formation of transformation products during their interaction with birnessite. This loss of antimicrobial efficacy was associated with specific chemical transformations, such as the opening of the piperazine ring for CIP and hydroxylation and demethylation for TC. Interestingly, denitrifying activity, quantified in terms of nitrate reduction rates, remained unaffected by both CIP and TC at low concentrations that did not impact bacterial growth. However, under certain conditions, specifically at low concentrations of CIP, the second step of denitrification-nitrite reduction-was hindered, leading to the accumulation of nitrite. Our findings highlight that the transformation products induced by the mineral-mediated reactions of CIP or TC lose the initial antibacterial activity observed in the parent compounds. This research contributes valuable insights into the intricate interplay between antibiotics, redox-active minerals, and microbial activity in environmental systems.

Contaminated groundwater is considered as one of the most important pathways of human exposure to the geogenic contaminants. Present study has been conducted in a part of Indus basin to investigate the presence and spatial distribution of arsenic (As) and other trace metals in groundwater. The As concentration varies from bdl-255.6 μg/L and 24.6% of the 73 collected groundwater samples have As above world health organization (WHO) guideline of 10 μg/L. High concentration of As is found along the newer alluvium of Ravi River. As is found with high bicarbonate (HCO3−) and Iron (Fe) and low nitrate (NO3−) indicating reductive dissolution of Fe bearing minerals. However, silicate weathering along with high sulphate (SO42) and positive oxidation-reduction potential (ORP) indicates mixed redox conditions. Weathering of minerals along with other major hydrogeochemical process are responsible for composition of groundwater. With 31.5% of the samples, sodium bicarbonate (Na–HCO3) is the major water facies followed by magnesium bicarbonate (Mg–HCO3) in 30% of samples. As, Fe and other trace metals including copper (Cu), cadmium (Cd), chromium (Cr), zinc (Zn) were used to calculate the health risk for children and adults in the region. Out of 73 samples, 58% has high Fe, 32.8% has high Zn, and 4.1% has high Cd which are above the prescribed limits of WHO guidelines. Health risk of the population has been assessed using chronic dose index (CDI), hazardous quotients (HQ) and hazardous index (HI) for children and adults. The mean CDI values follows the order as Fe > Zn > Cu > As > Cr > Cd, while the HQ values indicates high As hazards for both children and adults. 43.8% of the groundwater samples have high HI for adults, however, 49.3% has high HI for children indicating higher risk for children compared to adults. A large-scale testing should be prioritized to test the wells for As and other trace metals in the study region to reduce health risks.

The sorption behaviour of three perfluoroalkyl substances (PFASs), namely perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonic acid (PFHxS), was determined on 28 tropical soils. Tropical soils are often highly weathered, richer in sesquioxides than temperate soils and may contain variable charge minerals. There are little data on sorption of PFASs in tropical soils. The highest Kd values were found for PFOS with mean values ranging from 0 to 31.6 L/kg. The Kd values for PFOA and PFHxS ranged from 0 to 4.9 L/kg and from 0 to 5.6 L/kg, respectively. While these values are in the range of literature sorption data, the average Kd values for PFOS and PFOA from the literature were 3.7 times and 3.6 times higher, respectively, than those measured in this study. Stepwise regression analysis did explain some of the variance, but with different explanatory variables for the different PFASs. The main soil properties explaining sorption for PFOS and PFOA were oxalate-extractable Al and pH, and for PFHxS was pH.

The Tharsis mine is presently abandoned, but the past intense exploitation has left large dumps and other sulphide-rich mining wastes in the area generating acid mine drainages (AMD). The main goal of this work is to study the effect of hydrogeochemical processes, hydrological regime and the waste typology on the physicochemical parameters and dissolved concentrations of pollutants in a deeply AMD-affected zone. Extreme leachates are produced in the area, reaching even negative pH and concentrations of up to 2.2 g/L of As and 194 g/L of Fe. The results of the comparison of ore grades of sulphide deposits with dissolved concentrations in waters shows that Pb is the least mobile element in dissolution probably due to the precipitation of Pb secondary minerals and/or its coprecipitation on Fe oxyhydroxysulphates. Arsenic, Cr, and V are also coprecipitated with Fe minerals. Seasonal patterns in metal contents were identified: elements coming from the host rocks, such as Al, Mn and Ni, show their maximum values in the dry period, when dilution with freshwater is lower and the interaction of water-rock processes and evaporation is higher. On the other hand, As, Cr, Fe, Pb and V show minimum concentrations in the dry period due to intense Fe oxyhydroxysulphate precipitation. In this sense, large sulphide rich waste heaps would be a temporal sink of these elements (i.e. Pb, As, Cr and V) in the dry period, and a significant source upon intense rainfalls.

Elevated inorganic arsenic concentrations in groundwater has become a major public and environmental health concern in different parts of the world. Currently, As-contaminated groundwater issue in many countries and regions is a major topic for publications at global level. However, there are many regions worldwide where the problem has still not been resolved or fully understood due to inadequate hydrogeochemical investigations. Hence, this study evaluates for the first time the hydrogeochemical behavior of the arid and previously unexplored inland basin of Sirjan Plain, south east (SE) Iran, in order to assess the controlling factors which influence arsenic (As) mobility and its distribution through groundwater resources. Total inorganic arsenic concentration was measured using inductive-coupled plasma optical emission spectrometry (ICP-OES). Arsenic content in groundwater of this region ranged between 2.4 and 545.8 μg/L (mean value: 86.6 μg/L) and 50% of the samples exceeded the World Health Organization (WHO) guideline value of 10 μg/L in drinking water. Groundwater was mainly of Na-Cl type and alkaline due to silicate weathering, ion exchange and evaporation in arid conditions. Elevated As concentrations were generally observed under weakly alkaline to alkaline conditions (pH > 7.4). Multivariate statistical analysis including cluster analysis and bi-plot grouped As with pH and HCO3 and demonstrated that the secondary minerals including oxyhydroxides of Fe are the main source of As in groundwater in this region. The desorption of As from these mineral phases occurs under alkaline conditions in oxidizing arid environments thereby leading to high levels of As in groundwater. Moreover, evaporation, ion exchange and saltwater intrusion were the secondary processes accelerating As release and its mobility in groundwater. Based on the results of this study, desorption of As from metal oxy-hydroxides surfaces under alkaline conditions, evaporation and intrusion of As-rich saline water are considered to be the major factors causing As enrichment in arid inland basins such as those in southeast Iran. This study proposes the regular monitoring and proper groundwater management practices to mitigate high levels of arsenic in groundwater and related drinking water wells of Sirjan Plain.

Phytostabilization of sulfidic PbZn tailing landscapes may be one of interim options of tailings management, but which is limited by acute phytotoxicity of heavy metals in the tailings. The present study aimed to investigate the effectiveness of soluble phosphate (i.e., K2HPO4) in immobilizing soluble Pb, Cd and Zn and lowering their acute phytotoxicity. The addition of soluble phosphate improved the growth of native plants Acacia chisholmii and survival rate of A. ligulata, where the latter exhibited 100% survival rate. This was in contrast to effects of conventional organic amendment in the tailings on metal solubility (e.g., elevated metal levels in porewater) and plant survival (e.g., only 42%). Organic amendment with mulch did not lower the levels of water-soluble Cd, Pb and Zn and their concentrations in plant tissues after 56 days of plant growth in the treatment. In contrast, the tailings amended with K2HPO4 significantly decreased metal concentrations in the porewater and plant tissues by about 80–92% and 56–88%, respectively. The metal immobilization by phosphate was due to the formation of insoluble or sparingly soluble metal (Pb, Cd and Zn)-phosphate minerals in the tailings with circumneutral pH conditions, as revealed by using X-ray diffraction and scanning electron microanalyses. The reduced metal concentrations in roots and shoots of Acacia species after direct root contact with the K2HPO4 amended tailings suggested that metals (i.e., Pb, Cd and Zn) were effectively immobilized by the phosphate treatment of the tailings. These findings indicate that addition of high dosage of soluble phosphate may provide a low cost option to treat sulfidic PbZn tailings for rapid phytostabilization of the tailings surface, as an interim option to manage environmental risks of sulfidic PbZn tailings.

High arsenic (As) concentrations in the soil, water and plant systems can pose a direct health risk to humans and ecosystems. Phosphate (Pi) ions strongly influence As availability in soil, its uptake and toxicity to plants. Better understanding of As(V)-Pi interactions in soils and plants will facilitate a potential remediation strategy for As contaminated soils, reducing As uptake by crop plants and toxicity to human populations via manipulation of soil Pi content. However, the As(V)-Pi interactions in soil-plant systems are complex, leading to contradictory findings among different studies. Therefore, this review investigates the role of soil type, soil properties, minerals, Pi levels in soil and plant, Pi transporters, mycorrhizal association and microbial activities on As-Pi interactions in soils and hydroponics, and uptake by plants, elucidate the key mechanisms, identify key knowledge gaps and recommend new research directions. Although Pi suppresses As uptake by plants in hydroponic systems, in soils it could either increase or decrease As availability and toxicity to plants depending on the soil types, properties and charge characteristics. In soil, As(V) availability is typically increased by the addition of Pi. At the root surface, the Pi transport system has high affinity for Pi over As(V). However, Pi concentration in plant influences the As transport from roots to shoots. Mycorrhizal association may reduce As uptake via a physiological shift to the mycorrhizal uptake pathway, which has a greater affinity for Pi over As(V) than the root epidermal uptake pathway.

Emission of hazardous trace elements (HTEs) from energy production is receiving much attention due to concerns about the toxicity to the ecosystem and human health. This study presented new field measurement data on the HTEs partitioning behavior and size-segregated elemental compositions of gaseous particular matter (PM) generated from a commercial circulating fluidized bed (CFB) power plant. Mineralogical and morphological characteristics of combustion ash and PM2.5 (particle diameter less than 2.5 μm) were determined by X-ray diffractometer (XRD) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS). Functional groups alteration during CFB combustion was characterized by Fourier transform infrared spectroscopy (FTIR). The presence of aliphatic hydrogen at 2910 cm−1 and 2847 cm−1 in the PM2.5 suggested that the aliphatic carbon-rich volatiles were absorbed on the fine particles with large surface area. Fine fly ash (PM2.5) occurred as irregular glass particles or/and as unburned carbon. The typical irregular particles were mainly composed of Al-Si-Ca or Al-Si-Fe phases. The enrichment behavior of HTEs was determined for the airborne size-segregated particular matter. Elemental occurrences, combustion temperature, unburnt carbon, and limestone additives during CFB combustion were critical in the transformation behavior of HTEs. The total potentially mobile pollutants that exit the CFB power plant every year were estimated as follows: 0.22 tons of Cr, 0.12 tons of Co, 0.73 tons of Ni, 0.04 tons of As, 0.07 tons of Se, 3.95 kg of Cd, and 3.34 kg of Sb.

The purpose of this pilot study was to test spider webs as a fast tool for magnetic biomonitoring of air pollution. The study involved the investigation of webs made by four types of spiders: Pholcus phalangioides (Pholcidae), Eratigena atrica and Agelena labirynthica (Agelenidae) and Linyphia triangularis (Linyphiidae). These webs were obtained from outdoor and indoor study sites. Compared to the clean reference webs, an increase was observed in the values of magnetic susceptibility in the webs sampled from both indoor and outdoor sites, which indicates contamination by anthropogenically produced pollution particles that contain ferrimagnetic iron minerals. This pilot study has demonstrated that spider webs are able to capture particulate matter in a manner that is equivalent to flora-based bioindicators applied to date (such as mosses, lichens, leaves). They also have additional advantages; for example, they can be generated in isolated clean habitats, and exposure can be monitored in indoor and outdoor locations, at any height and for any period of time. Moreover, webs are ubiquitous in an anthropogenic, heavily polluted environment, and they can be exposed throughout the year. As spider webs accumulate pollutants to which humans are exposed, they become a reliable source of information about the quality of the environment. Therefore, spider webs are recommended for magnetic biomonitoring of airborne pollution and for the assessment of the environment because they are non-destructive, low-cost, sensitive and efficient.

Arsenic (As) contamination is a global problem. Straw incorporation is widely performed in As contaminated paddy fields. To understand how straw and straw biochar incorporation affect As transformation and translocation in the soil-microbe-rice system, a pot experiment was carried out with different dosages of rice straw and straw biochar application. Results showed that both straw biochar and straw application significantly increased As mobility. Straw biochar mobilized As mainly through increasing soil pH and DOM content. Straw incorporation mainly through enhancing As release from iron (Fe) minerals and arsenate (As(V)) reduction to arsenite (As(III)). Straw biochar didn't significantly affect As methylation, while straw incorporation significantly enhanced As methylation, elevated dimethylarsenate (DMA) concentration in soil porewater and increased As volatilization. Straw biochar didn't significantly change total As accumulation in rice grains, but decreased As(III) accumulation by silicon (Si) inhibition. Straw incorporation significantly increased DMA, but decreased As(III) concentration in rice grains. After biochar application, dissolved As was significantly positively correlated with the abundance of Bacillus, indicating that Bacillus might be involved in As release, and As(III) concentration in polished grains was negatively correlated with Si concentration. The significant positive correlation between dissolved As with Fe and the abundance of iron-reducing bacteria suggested the coupling of As and Fe reduction mediated by iron-reducing bacteria. The significant positive correlation between DMA in rice grains and the abundance of methanogenic bacteria indicated that methanogenic bacteria could be involved in As methylation after straw application. The results of this study would advance the understanding how rice straw incorporation affects As fate in soil-microbe-rice system, and provide some guidance to straw incorporation in As contaminated paddy soil. This study also revealed a wealth of microorganisms in the soil environment that dominate As mobility and transformation after straw incorporation.