Exposure risk assessment to organic compounds based on their concentrations in return water from shale gas developments.

Because of shale gas operations, significant amounts of return water from hydraulic fracturing are stored in tanks and/or ponds on the surface. These waters contain varying concentrations of toxic organic compounds; hence, there is reasonable concern about the occurrence of hypothetical leakages, which would cause adverse environmental effects and pose a risk to human health. In this study, the chronic and acute carcinogenic and non-carcinogenic risks from exposure to these pollutants by inhalation, ingestion and dermal contact have been assessed for an affected area. The first part of this study focused on estimating the concentrations of organic compounds in the water-soil-atmosphere system. These models are of a general nature and can be applied to any site. In this study, they are applied to the Marcellus shale formation. The analyses developed in this work show that the risks - both carcinogenic and non-carcinogenic - regarding the inhalation of volatile organic compounds (VOCs) increase rapidly and exceed the acceptable thresholds by several orders of magnitude in all scenarios, irrespective of the different recharge rates considered. Given that the hypothetical leakage under consideration occurs at a depth of 50 cm, in the buried part of a semi-buried tank-type reservoir, the direct contamination via wastewater of the most superficial parts of the soil is less likely, and soil particles are generally widely dispersed in air before inhaling. Moreover, the sensitivity analysis indicated that the variable contributing the most to the determined risk levels was the pollutant concentration, followed by the exposure time. Therefore, using appropriate technology to reduce pollutant concentrations in storage ponds is the best strategy to minimise the associated risk to human health.

Appraisal of groundwater contamination from surface spills of fluids associated with hydraulic fracturing operations.

Contaminated groundwater is a priority issue on the environmental agendas of developed countries. Therefore, there is an obvious need to develop instruments and decision-making mechanisms that allow the estimation of the risk to human health due to the presence of contaminants in soils and groundwater, in a fast and reliable manner. Thus, this study aims to assess whether the spilling of hydraulic fracturing fluids prior to injection has a potential risk to groundwater quality in the Kern County Sub-basin, California, by identifying the hydrological factors and solute transport characteristics that control these risks while taking into consideration the temperature rises due to climate change. The approach uses the concept of the groundwater pollution risk based on comparing the concentration of pollutants within the water table by using a predetermined permissible level. The current average annual temperature and that by the end of the 21st century was used to estimate the diffusion of benzene through three types of soil by using HYDRUS-1D software. The software was used to predict the contaminant concentration profile of benzene in the water table with special reference to the impact of surface temperatures. The results showed that an expected rise of the surface temperature by 4.3 °C led to an increase in the concentration of benzene by 2.3 µg/l in sandy loam soil, 6.8 µg/l in silt loam soil, and finally, 2.6 µg/l in loam soil. The results show that climate change can substantially affect soil properties and their chemical constituents, which then play a major role in absorbing pollutants.

Forecasting concentrations of organic chemicals in the vadose zone caused by spills of hydraulic fracturing wastewater.

The return water from hydraulic fracturing operations is characterised by high concentrations of salts and toxic organic compounds. This water is stored on the surface in storage tanks and/or ponds. Wastewater spills caused by inappropriate storage can lead to the contamination of various environmental compartments, thus posing a risk to human health. Such risk can be determined by estimating the concentrations of the substances in the storage system and the behaviour of the same in function of the characteristics of the environment in which they are released. To this end, here we addressed the evolution of the concentrations of pollutants in a tank used to store wastewater from hydraulic fracturing operations. To do this, we estimated both the volume of flowback and the concentrations of the pollutants found in these waters. We then examined the dynamic behaviour of spill-derived compounds in the various environmental compartments in function of the conditions of the medium (humid, semi-arid, and arid). This approach allowed us to rank the hazard posed by the chemical compounds in question, as well as to determine those parameters associated with both the compounds and external natural conditions that contribute to environmental risk. Our results shed greater light on the mechanism by which external environmental variables (especially recharge rate) influence the migration of organic compounds in the vadose zone, and contribute to the prediction of their concentrations. Also, by estimating the time that chemicals remain in contaminated areas, we identify the phases of contamination that pose the greatest risk to human health. In summary, the approach used herein allows the ranking of compounds on the basis of risk to human health and can thus facilitate the design of pollutant management strategies. Of note, our ranked list highlights the relevance of benzene.

Statistical evaluation of the geochemical variability in overbank sediments in Spain.

The overall objective of this study is to estimate, detect and specify the main sources of variance which affect the contents of the different elements in overbank sediments across Spain. These sources of variance were assessed and compared by means of a series of analyses of variance (ANOVAs), by regarding two parameters: their significance and their contribution to the total variance. Overbank sediments, sampled in erosion banks, were studied in several locations, in basins which drain different types of geological backgrounds and land uses (urban, mining, agricultural or pristine) across the Iberian Peninsula. Forty-eight elements (mostly in the < 63 µm fraction) were analysed by ICP-OES, ICP-MS and INAA. After an isometric log ratio (ilr) transformation of the data, three ANOVA analyses were performed considering three perspectives: (1) local scale, (2) regional scale: within-profile perspective and (3) regional scale: inter-profile perspective. On a local scale, it was observed that the variability of rare earth elements (REE) depends mostly on the grain size and that heavy metals are also influenced by depth. In the analysis carried out on a regional scale, from a within-profile perspective, depth and duplicates do not influence significantly the variability of the element contents. Finally, from an inter-profile perspective, the selected sources of variance were land use and provenance, whose significance is the highest. While grain size and the selection of depth are of crucial importance in the final results, on local studies, land use and provenance are the ones that influence the most the composition of sediments in regional studies.

A model for predicting organic compounds concentration change in water associated with horizontal hydraulic fracturing.

Horizontal drilling and hydraulic fracturing are technologies designed to increase natural gas flow and to improve productivity in low permeability formations. During this drilling operation, tons of flowback and produced water, which contain several organic compounds, return to the surface with a potential risk of influencing the surrounding environment and human health. In order to conduct predictive risk assessments a mathematical model is needed to evaluate organic compound behaviour along the water transportation process as well as concentration changes over time throughout the operational life cycle. A comprehensive model, which fits the experimental data, combining an Organic Matter Transport Dynamic Model with a Two-Compartment First-order Rate Constant (TFRC) Model has been established to quantify the organic compounds concentrations. This algorithm model incorporates two transportation rates, fast and slow. The results show that the higher the value of the organic carbon partition coefficient (koc) in chemicals, the later the maximum concentration in water will be reached. The maximum concentration percentage would reach up to 90% of the available concentration of each compound in shale formation (whose origin may be associated to drilling fluid, connate water and/or rock matrix) over a sufficiently long period of time. This model could serve as a contribution to enhance monitoring strategy, increase benefits out of optimizing health risk assessment for local residents and provide initial baseline data to further operations.

Application of lead isotopic methods to the study of the anthropogenic lead provenance in Spanish overbank floodplain deposits.

Changes in the principal sources of Pb in overbank sediment profiles have been documented for two Spanish areas by using Pb isotopes and Pb concentrations. These locations (Madrid and Tinto-Odiel basin) represent two of the most contaminated regions in Spain. The Community of Madrid is characterized by heavy industrial and urban activity, focused mainly in Madrid City. The Tinto-Odiel basin drains the Iberian Pyrite Belt, which hosts many polymetallic massive sulphides and is heavily affected by mining activities in their headwaters. It has been proven that the influence of anthropogenic activity is reflected in these overbank deposits by variations in Pb concentrations that, in general, correlate with shifts in the (206)Pb/(207)Pb ratio. Rivas profile (downstream of Madrid) was found to be the most anthropogenically influenced site. The sediments within this profile which were recently deposited (170 ± 40 years BP) have the least radiogenic signatures. (206)Pb/(207)Pb ratios ranged between 1.1763 and 1.1876 indicating significant contributions of anthropogenic Pb. In contrast, profiles upstream of Madrid possess an average (206)Pb/(207)Pb ratio of 1.2272. It is difficult to clearly identify the most prominent source as the sediments appear to be characterized by an input from several sources. The floodplain profiles in the Tinto-Odiel basin exhibit uniform (206)Pb/(207)Pb ratios ranging from 1.1627 (Odiel river) to 1.1665 (Tinto river). These ratios are similar to the ones possessed by sulphide ores in the area and differ from the ratios of other nonmineralized formations in the basin, indicating that mining activities are the primary, if not sole, source of Pb to the sediments.

A geochemical study of overbank sediments in an urban area (Madrid, Spain).

Overbank and stream sediments have been studied in the Community of Madrid. Four vertical profiles have been sampled corresponding to Guadarrama, Jarama, and finally Manzanares River, where two profiles have been studied upstream (El Pardo profile) and downstream (Rivas profile) Madrid city. Sieved samples (<63 µm) were subjected to total (ICP-MS/ICP-OES and INAA) and partial analysis (ICP-MS). AMS radiocarbon dating techniques revealed a young age (170 ± 40 years BP) at 2.40-2.65 m depth for Rivas profile. It has not been possible to detect pristine or pre-industrial overbank sediments, since in the rest of the studied profiles, anthropogenic wastes were found even in the lower levels. Three main sources of sediment have been detected in the area. Granitic and arkosic geology, located in the northern part of Madrid (U, Th, W, K, Na, or rare earth elements); clays located in the southeast of Madrid (Ni, Cr, or V), and finally an anthropogenic source has been identified (Au, Ag, Pb, Zn, or Sb) in Rivas profile. The influence of the anthropogenic activity has been established based on the contents distribution of contaminant elements in the profile. This can be associated to the growth of industrial activities and population in the city of Madrid during the last decades. The comparison of the profiles by a k-means cluster analysis showed some similarities for these samples that could have analogous sources (anthropogenic and geological).