Measuring Pb isotope ratios in fresh snow filtrate refines the apportioning of contaminant sources in the Arctic.

The remoteness and low population in the Arctic allow us to study global environmental processes, where the analysis of indicators can provide useful information about local and distant pollution sources. Fresh snow represents a convenient indicator of regional and transboundary atmospheric contamination sources, entrapping aerosols, and particulates like a natural autosampler of the environment. Lead stable isotopes are widely used to trace and monitor local and distant pollution sources. However, the behavior of Pb within different snow components is still not thoroughly studied, and its significance could be underestimated if only larger particulates are accounted for. We collected snow and samples from potential sources (fuel, rocks, coal) in three Arctic localities: Nuuk (Greenland), Reykjavik (Iceland), and Longyearbyen (Svalbard). We separated the filtrate from the filter residue through 0.45 µm nitrocellulose membranes to isolate the low-diameter particles associated with long-range transport from larger particles of mostly local natural origin. Filtrates yielded higher EFs (enrichment factor as the Pb/Al ratio relative to the upper crust) than filtration residues (80 ± 104 and 2.1 ± 1.1, respectively), and Pb isotope signals similar to fuel and coal (206Pb/207Pb are 1.199 ± 0.028 in coal, 1.168 ± 0.029 in filtrates, 1.163 ± 0.013 in fuel, 1.137 ± 0.045 in residues, and 0.985 ± 0.020 in rocks). In contrast to filtrates, the filter residues present wider ranges of Pb isotope compositions and crustal contributions and lower EFs, so we suggest that filtrate contains Pb from fuel combustion more selectively, while the residue carries a more considerable contribution of local mineral dust that can mask the contribution of other anthropogenic or distant natural sources. These findings add weight to the notion that filtrates are a more selective measure of metal deposition from long-range anthropogenic emissions compared to analyzing bulk melted snow or only filter residues.

Pyrolysis temperature influences the capacity of biochar to immobilize copper and arsenic in mining soil remediation.

Biochar is a promising material used for multiple remediation approaches, mainly in polluted soils. Its properties can differ depending on feedstock and pyrolysis temperature. In this context, we tested the capacity of three biochar products made from corncob, pyrolyzed at different temperatures (350, 500, and 650 °C), to remediate a mining soil affected by high levels of Cu and As. We performed an exhaustive characterization of the biochar. We found that biochar showed a higher surface area with increasing pyrolysis temperature, whereas high molecular weight PAHs were detected in biochar produced at the maximum temperature, thus indicating potential ecotoxicological risks. After the application of biochar to the soil, Cu was partially immobilized, especially when using that obtained at 500 °C. This effect is attributed to the structure of this material and an increase in soil pH and organic matter content. Conversely, As was increased in the soluble fraction for all three types of biochar but in a proportion that lacks relevance. On the whole, given its lower PAH content, higher Cu immobilization ratio, and an almost negligible increase in As availability, biochar obtained at 500 °C outperformed the other two products with respect to soil recovery. Of note, data on Cu and As availability were doubled-checked using two extraction methodologies. We propose that this operational approach for determining the most suitable pyrolysis temperature will find application in other soil remediation actions.

Effective bioremediation of soil from the Burgan oil field (Kuwait) using compost: A comprehensive hydrocarbon and DNA fingerprinting study.

An innovative combination of metagenomic profiling of microbial communities and GC-MS & Pyrolysis-GC-MS fingerprinting methods were used to assess the biodegradation of contaminated soil from the Burgan oil field in Kuwait. The soil was treated with (sludge) compost in microcosms to evaluate the feasibility of this material for bioremediation purposes. The most favourable trial showed a > 80% decrease in TPH, thereby indicating strong potential for full-scale application using a cost-effective technology and thus in line with the principles of the circular economy. The microbial study showed that compost addition enhanced the organic matter and nutrient content of the soil. However, the microorganisms in the compost did not seem to play a relevant role in bioremediation, meaning that compost amendments serve as a biostimulation rather than a bioaugmentation approach. The chemical study of the distinct oil fractions revealed rapidly biodegraded compounds (alkanes, alkyl-aromatics, etc.) and others that were much more refractory (hopanes, benzohopanes, etc.). Of note, although heavy fractions are usually considered recalcitrant to biodegradation, we observed incipient degradation of the asphaltene fraction by means of double-shot thermodesorption and pyrolysis. Finally, chemical fingerprinting also revealed that the treated soil contained some of the compounds found in the compost, such as coprostanol, cholesterol, and plant sterols. This observation would support the use of these compounds as proxies to monitor the effects of compost and to adjust dosages in real-scale bioremediation treatments.

Interplay between arsenic and selenium biomineralization in Shewanella sp. O23S.

Bacteria play crucial roles in the biogeochemical cycle of arsenic (As) and selenium (Se) as these elements are metabolized via detoxification, energy generation (anaerobic respiration) and biosynthesis (e.g. selenocysteine) strategies. To date, arsenic and selenium biomineralization in bacteria were studied separately. In this study, the anaerobic metabolism of As and Se in Shewanella sp. O23S was investigated separately and mixed, with an emphasis put on the biomineralization products of this process. Multiple analytical techniques including ICP-MS, TEM-EDS, XRD, Micro-Raman, spectrophotometry and surface charge (zeta potential) were employed. Shewanella sp. O23S is capable of reducing selenate (SeO42-) and selenite (SeO32-) to red Se(-S)0, and arsenate (AsO43-) to arsenite (AsO33-). The release of H2S from cysteine led to the precipitation of AsS minerals: nanorod AsS and granular As2S3. When As and Se oxyanions were mixed, both As-S and Se(-S)0 biominerals were synthesized. All biominerals were extracellular, amorphous and presented a negative surface charge (-24 to -38 mV). Kinetic analysis indicated the following reduction yields: SeO32- (90%), AsO43- (60%), and SeO42- (<10%). The mix of SeO32- with AsO43- led to a decrease in As removal to 30%, while Se reduction yield was unaffected (88%). Interestingly, SeO42- incubated with AsO43- boosted the Se removal (71%). The exclusive extracellular formation of As and Se biominerals might indicate an extracellular respiratory process characteristic of various Shewanella species and strains. This is the first study documenting a complex interplay between As and Se oxyanions: selenite decreased arsenate reduction, whereas arsenate stimulated selenate reduction. Further investigation needs to clarify whether Shewanella sp. O23S employs multi-substrate respiratory enzymes or separate, high affinity enzymes for As and Se oxyanion respiration.

Short-term experiment for the in situ stabilization of a polluted soil using mining and biomass waste.

Mining and biomass waste were used to remediate a brownfield affected by As, Cd, Cu, Pb and Zn pollution in a pilot scale experiment, and a plant used for phytoremediation purposes was used as an indicator of possible toxicological effects. To carry out the experiments, plots in field conditions were treated with magnesite (mining waste), magnesite-sludge compost, and magnesite-biochar respectively, while untreated soil was used as a control. The plots were then irrigated and left for one week, after which seeds of the ryegrass Lolium perenne L. were sown. Soil properties such as metal(loid) availability, pH, phosphorus availability, total nitrogen, organic carbon, and nutrients were monitored for two months. Finally, the ryegrass was harvested and pollutant concentrations were analyzed in the aerial parts. Magnesite proved to be an excellent amendment for metal(loid) immobilization, although the notable increase in soil pH and Mg content inhibited plant growth. However, the application of magnesite in combination with the sludge compost (rich in N and P) favored plant growth and also immobilized metals, although As availability increased. In contrast, the analysis of plants in this treatment revealed lower As and metal concentrations than those grown in the untreated soil. In turn, the application of magnesite and biochar was also effective in reducing metal(loid) availability; however, the plants did not grow under these conditions, probably due to the low N and P content of biochar. In this regard, the combined application of mining waste and sludge compost emerges as a useful nature-based solution for soil remediation in the context of the circular economy.

Comparison of the effectiveness of biochar vs. magnesite amendments to immobilize metals and restore a polluted soil.

Here we addressed the remediation of a soil severely contaminated by Cu, Cd, Pb and Zn. In this regard, we tested the capacity of magnesite and biochar, inorganic and organic soil amendments, respectively, to reduce metal availability and improve soil properties. To this end, 1-kg pots containing the polluted soil were amended with either magnesite or biochar. Metal availability and soil properties were then measured at days 15 and 75. Also, to evaluate the impact of the two treatments on plant growth, we conducted experimental trials with Brassica juncea L. and compost addition. Both amendments, but particularly magnesite, markedly decreased metal availability. Soil properties were also enhanced, as reflected by increases in the cation exchangeable capacity. However, plant growth was inhibited by magnesite amendment. This observation could be attributable to an increase in soil pH and cation exchange capacity as well as a high Mg concentration. In contrast, biochar increased biomass production but decreased the quantity of metals recovered when the plants are harvested. In conclusion, on the basis of our results, we propose magnesite as a suitable approach for stabilizing contaminated soils (or even spoil heaps) where revegetation is not a priority. In contrast, although biochar has a lower, but still significant, capacity to immobilize metals, it can be used to restore natural soil properties and thus favor plant growth.

Effects of in situ Remediation With Nanoscale Zero Valence Iron on the Physicochemical Conditions and Bacterial Communities of Groundwater Contaminated With Arsenic.

Nanoscale Zero-Valent Iron (nZVI) is a cost-effective nanomaterial that is widely used to remove a broad range of metal(loid)s and organic contaminants from soil and groundwater. In some cases, this material alters the taxonomic and functional composition of the bacterial communities present in these matrices; however, there is no conclusive data that can be generalized to all scenarios. Here we studied the effect of nZVI application in situ on groundwater from the site of an abandoned fertilizer factory in Asturias, Spain, mainly polluted with arsenic (As). The geochemical characteristics of the water correspond to a microaerophilic and oligotrophic environment. Physico-chemical and microbiological (cultured and total bacterial diversity) parameters were monitored before and after nZVI application over six months. nZVI treatment led to a marked increase in Fe(II) concentration and a notable fall in the oxidation-reduction potential during the first month of treatment. A substantial decrease in the concentration of As during the first days of treatment was observed, although strong fluctuations were subsequently detected in most of the wells throughout the six-month experiment. The possible toxic effects of nZVI on groundwater bacteria could not be clearly determined from direct observation of those bacteria after staining with viability dyes. The number of cultured bacteria increased during the first two weeks of the treatment, although this was followed by a continuous decrease for the following two weeks, reaching levels moderately below the initial number at the end of sampling, and by changes in their taxonomic composition. Most bacteria were tolerant to high As(V) concentrations and showed the presence of diverse As resistance genes. A more complete study of the structure and diversity of the bacterial community in the groundwater using automated ribosomal intergenic spacer analysis (ARISA) and sequencing of the 16S rRNA amplicons by Illumina confirmed significant alterations in its composition, with a reduction in richness and diversity (the latter evidenced by Illumina data) after treatment with nZVI. The anaerobic conditions stimulated by treatment favored the development of sulfate-reducing bacteria, thereby opening up the possibility to achieve more efficient removal of As.

Application of biochar, compost and ZVI nanoparticles for the remediation of As, Cu, Pb and Zn polluted soil.

Here we tested the capacity of zero valent iron nanoparticles (nZVI) combined with two organic amendments, namely, compost and biochar, to immobilize metal(oid)s such as As, Cu, Pb, and Zn. In addition, the effects of the amendments on the development of Brassica juncea L., a plant widely used for phytoremediation purposes, were also examined. To perform the experiments, pots containing polluted soil were treated with nZVI, compost-biochar, or a blend of compost-biochar-nZVI. Metal(oid)s availability and soil properties were evaluated after 15 and 75 days, and the height and weight of the plants were measured to determine development. The compost-biochar amendment showed excellent capacity to immobilize metals, but As availability was considerably increased. However, the addition of nZVI to the mixture corrected this effect considerably. In addition, soil treatment with nZVI alone led to a slight increase in Cu availability, which was not observed for the mixture with organic amendments. With respect to soil properties, the CEC and pH were enhanced by the compost-biochar amendment, thereby favoring plant growth. Nevertheless, the nanoparticles reduced the concentration of available P, which impaired plant growth to a certain extent. In conclusion, Fe-based nanoparticles combined with organic amendments emerge as powerful approaches to remediate soils contaminated by metals and metalloids.

Nanoremediation of As and metals polluted soils by means of graphene oxide nanoparticles.

The capacity of graphene oxide nanoparticles (nGOx) to reduce or increase As and metals availability in polluted soils was compared with that of zero valent iron nanoparticles (nZVI). The nanomaterials used in this study were characterized by X-ray techniques, CHNS-O analysis, dynamic light scattering, and microscopy procedures such as atomic force microscopy. To assess the capacity of these materials to immobilize pollutants, field samples of two soils were treated with nZVI and nGOx at a range of doses (0.2%, 1% and 5%). Availability tests were then performed. nGOx effectively immobilized Cu, Pb and Cd, but mobilized As and P (even at low doses), in the latter case irrespective of the simultaneous presence of high concentrations of metals. In turn, nZVI promoted notable immobilization results for As and Pb, a poorer result for Cd, and an increased availability for Cu. Soil pH and EC have been slightly affected by nGOx. On the whole, nGOx emerges as a promising option for mobilization/immobilization strategies for soil nanoremediation when combined with other techniques such as phytoremediation.

Arsenic release from pyrite ash waste over an active hydrogeological system and its effects on water quality.

Arsenic is a potentially toxic element of concern for environmental compartments, and it is a frequent pollutant in many abandoned industrial sites. In this study, geochemical and hydrogeological tools were used to determine the long-term effects of As-rich pyrite ash disposal (83,000 m3 as estimated by geostatistical tools) in a brownfield located over a quaternary alluvial aquifer. Throughout the site, soil pollution and water table oscillation led to leachates in the form of both run-off and infiltration waters, thereby reducing (ground)water quality (e.g. pH, electrical conductivity) and, in particular, increasing the concentration of arsenic (average approx. 4000 µg/l for one hydrological year). By means of laboratory and in situ measurements, the main mechanisms through which the sulphide remaining in the pyrite ash leaches were identified. In addition, to evaluate the effects of the polluted groundwater on the nearby main river, a mathematical approach using the Domenico analytical groundwater transport model revealed potential concentrations of 49 µg/l of arsenic in the junction between the study aquifer and the river, equivalent to an annual quantity of 49 kg of this element.

Contribution of fluorite mining waste to mercury contamination in coastal systems.

Samples from 13 beaches along the northern Spanish coast, a region with a history of heavy industries, were first screened to identify signs of pollution. High concentrations of Hg and Ba on Vega beach were found, both elements belong to the fluorite ore paragenesis, mined in the surroundings. Samples of beach and fluvial sediments, and nearby soils were collected in Vega beach area to address potential Hg pollution, fate and sources. Most samples showed a similar pollutants fingerprint to that of beach samples, especially those taken from white dunes, registering notable Hg concentrations. Hg was enriched in the finer fractions, and overall the main input was attributed to the mining waste discharged along the coast in the past. Although a specific risk assessment and study of the submerged sediments are advisable for this area, Hg bioavailability and methylation were low, thus indicating that this metal poses a reduced environmental risk.

A multivariate examination of the timing and accumulation of potentially toxic elements at Las Conchas bog (NW Spain).

The inorganic content of the well-preserved 3.2-m record of Las Conchas bog (NW Spain), covering 8000 cal yr BP., was analysed. To study natural vs. human contributions, we applied an innovative approach, namely the sequential study of multivariate statistics (factor analysis followed by clustering of the factor score matrix) and enrichment factors (EFs). The increasing weight of potentially toxic elements (PTEs) such as the geochemical association of Zn, Pb and Cd (EFs higher than 10, 20 and 40 in the last two centuries) was revealed, and corroborated by the contrast between the contents of anthropogenic Pb and total Rare Earth Elements (a suitable proxy for natural geogenic supplies). Furthermore, elements such as Hg, Tl and As also showed enrichment in the most recent samples of the study core. Some of them are commonly associated with global atmospheric transport; however, in this case, their increasing contents could also be explained by nearby industrial and mining activities. In summary, severe pollution was observed in the uppermost part of the record, thereby pointing to an important environmental concern. Given that local and regional sources of PTEs, such as mining and heavy industry, especially Zn smelting, were probably the main historical causes of this contamination and that some of these industries are still active, we consider that our findings deserve further attention.