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.

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.

Diagnostic ratios for the rapid evaluation of natural attenuation of heavy fuel oil pollution along shores.

Marine oil spills are typically followed by complex clean-up and monitoring operations of the shorelines affected. In this regard, determination of the changes in the chemical composition of the spilled product is crucial for evaluation purposes. The "GC-MS fingerprint" approach requires the identification of several key parameters in order to differentiate between weathering processes. In this context, we performed a 900-day study (eight sampling campaigns) of natural attenuation on a rocky shore affected by a heavy fuel oil spill. The residues coating the rocks were studied by extraction, separation and evaluation of SARA fractions, followed by GC-MS analysis for saturates and aromatics. The results identified a group of diagnostic ratios with irregular capabilities to differentiate between volatilization, photodegradation, and biodegradation (using n-alkanes, isoprenoids and PAHs), while a second group of primarily stable ratios (using dibenzothiphenes, tricyclics and hopanes) was also obtained. Notably, this is the first time that some of these ratios have been used for marine spill monitoring purposes. The ratios were applied not only to evaluate weathering at the study site, but also to obtain a comparison with the degradation of floating oil slicks-a demonstration that weathering of the latter was quicker than that of oil on the shore rocks. Additionally, Pyrolysis-GC-MS analysis of the asphaltene fraction of residues coating the rocks revealed moderate changes in the composition of this initially recalcitrant fraction. These changes were consistent with those found in the proportion of resins and asphaltene fractions over time.

Human health risk assessment in restoring safe and productive use of abandoned contaminated sites.

In Europe soil contamination has been recognized as a serious problem. The needs to remediate contaminated sites are not questionable, although the remediation actions are often hindered by their very high financial costs. On the other hand, the abandoned contaminated sites may have the potential for redevelopment and creating conditions appropriate for their productive reuse bringing social, economic and environmental benefits. The main concern associated with the contaminated sites is their potential adverse health impact. Therefore, in the process of contaminated site redevelopment the risk assessment and the subsequent risk management decisions will play a crucial role. The main objective of this study was to illustrate the role of the human health risk assessment (HRA) in supporting site remediation and reuse decisions. To exemplify the significance of the HRA process in this field the Nitrastur site, located in Asturias, Spain was used. Risks resulting from soil contamination with arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), mercury (Hg), zinc (Zn) and lead (Pb) were assessed under three potential future land use patterns: industrial, residential and recreational. The results of the study indicated that soil at the Nitrastur site might pose non-cancer and cancer risks to potential future receptors - industrial workers, residents and recreational users. Arsenic and lead are the main substances responsible for the health risk and the primary drivers of remedial decisions at the site. The highest total cancer risks were observed under the residential scenario, followed in descending order by the recreational and industrial ones. The remedial maps illustrate in which areas remediation activities are required, depending on a given land use pattern. The obtained results may be used to develop, analyse, compare and select the remedial options within the intended land use pattern. They may also be used to support the decisions concerning the reuse of the site or to create different redevelopment plans for different parts of the site. The study may help improve understanding and interaction between risk assessors and risk managers which are necessary to make proper, fully informed decisions enhancing public trust and credibility.

Reducing the mobility of arsenic in brownfield soil using stabilised zero-valent iron nanoparticles.

The use of nanoscale zero-valent iron (nZVI) as a new tool for the treatment of polluted soils and groundwater has received considerable attention in recent years due to its high reactivity, in situ application and cost-effectiveness. The objectives of this study were to investigate the effectiveness of using a commercial stabilised suspension of nZVI to immobilise As in brownfield soil and to investigate its impact on Fe availability in the treated soil. The phytotoxicities of the soil samples were also evaluated using a germination test with two plant species: barley (Hordeum vulgare L) and common vetch (Vicia sativa L). Two doses of the commercial nZVI suspension were studied, 1% and 10%, and two soil-nanoparticle interaction times, 72 h and 3 mo, were used to compare the stabilities of the soils treated with nZVI. The As availability was evaluated using a sequential extraction procedure and the toxicity characteristics leaching procedure (TCLP) test. The application of nZVI significantly decreased the availability of As in the soil. The immobilisation of As was more effective and more stable over time with the 10% dose than with the 1% dose of the commercial nZVI suspension. The application of nZVI did not induce an important increase in Fe mobility because the Fe leachability was less than 2 mg L(-1) over the time period studied. The lower availability of As in the soil led to a decrease in the phytotoxicity of the soil to barley and vetch germination. Thus, the proposed nanotechnology could be a potential alternative for the in situ remediation of As-polluted soils and could be combined with remediation processes where plants are involved.