Relating mercury occurrence in soil gases at establishments hosting children to historical mercury-using activities in Paris, France.

Volatile pollutants from former industrial sites can degrade the buildings' indoor air quality that were built after the industrial activities. Since 2010, environmental assessments have been conducted in French establishments hosting sensitive populations identified as being on or near potentially contaminated former industrial sites. These projects are based on historical studies traditionally carried out as part of managing contaminated sites, to determine which substances should be analyzed. They pinpoint former activities likely to have stored or used pollutants. We show that the historical information collected is not effective in targeting sites with increased probability of mercury being present in soil gases. Environmental history has demonstrated the existence of large-scale artisanal contamination, both prior to and concomitant with the industrial era. Classic historical studies would not take into account artisanal activities, which are less documented than industrial activities. We carried out additional research for three schools located in three different Parisian districts. Although information on activities which could have emitted mercury was relatively imprecise (in terms of location, type and duration of activities) and uncertainties exist about the completeness of the archival documents available, our investigations identified several mercury-using activities that had not been identified during the classic historical study. However, we have shown that the number of activities identified does not provide information on how mercury has affected soil gas. Consequently, although a more extensive historical research improves knowledge about the presence of potential mercury-using activities, our study shows that a systematic analysis of mercury as part of the assessment of establishments hosting sensitive populations remains relevant. This approach should be applied to other cities around the world.

Influence of agricultural amendments on arsenic biogeochemistry and phytotoxicity in a soil polluted by the destruction of arsenic-containing shells.

Agricultural soils can contain high arsenic (As) concentrations due to specific geological contexts or pollution. Fertilizer amendments could influence As speciation and mobility thus increasing its transfer to crops and its toxicity. In the present study, field-relevant amounts of fertilizers were applied to soils from a cultivated field that was a former ammunition-burning site. Potassium phosphate (KP), ammonium sulfate and organic matter (OM) were applied to these soils in laboratory experiments to assess their impact on As leaching, bioavailability to Lactuca sativa and microbial parameters. None of the fertilizers markedly influenced As speciation and mobility, although trends showed an increase of mobility with KP and a decrease of mobility with ammonium sulfate. Moreover, KP induced a small increase of As in Lactuca sativa, and the polluted soil amended with ammonium sulfate was significantly less phytotoxic than the un-amended soil. Most probable numbers of AsIII-oxidizing microbes and AsIII-oxidizing activity were strongly linked to As levels in water and soils. Ammonium sulfate negatively affected AsIII-oxidizing activity in the un-polluted soil. Whereas no significant effect on As speciation in water could be detected, amendments may have an impact in the long term.

Human health risks related to the consumption of foodstuffs of plant and animal origin produced on a site polluted by chemical munitions of the First World War.

Shells fired during World War I exhibited different explosive compounds and some of these weapons also contained a wide variety of chemical warfare agents. At the end of the war, for safety purposes, the large quantity of weapons remaining on the former front needed to be dismantled and destroyed. A large amount of the remaining shells was destroyed in specific sites which led to the contamination of the surroundings in Belgium and France. In the 1920s, 1.5 million chemical shells and 30,000 explosive shells were destroyed in a place close to the city of Verdun, in the East of France. In this paper, the risk for human health related to the consumption of foodstuffs produced on this site was assessed. To this end, food products of plant and animal origin were sampled in 2015-2016 and contaminant analyses were conducted. Human exposure was assessed using a specifically built methodology. The contaminants considered in this study were trace elements (TEs - primarily Zn, As, Pb and Cd), nitroaromatic explosives (trinitrotoluene, 2,4-dinitrotoluene, 2,6-dinitrotoluene, 2-amino-4,6-dinitroluene and 4-amino-2,6-dinitrotoluene), phenylarsenic compounds including diphenylarsinic acid and triphenylarsine, perchlorate, tetrabromoethane and vinyl bromide. Depending on the compound, different approaches were used to assess the risk for both adults and children. Exposure to these contaminants through the consumption of foodstuffs produced locally on the considered site was unlikely to be a health concern. However, as for inorganic arsenic, given the presence of highly contaminated zones, it was suggested that cereals should not be grown on certain plots.

An innovative application of stable isotopes (δ2H and δ18O) for tracing pollutant plumes in groundwater.

The identification of the sources of contaminants present in groundwater at industrial sites is primordial to address environmental and industrial issues. However, available tools are often inadequate or expensive. Here, we present the data of stable isotopes (δ18O and δ2H) of the water molecule at an industrial site where electrochemistry plant occurs impacting the groundwater quality. High ClO3 and ClO4 contents and 2H enrichment have been measured in groundwater. Recharge of aquifer relates to infiltration of rainwater and by subsurface inflow. On-site, industrial products are generated by electrolysis. We show that the electrolysis process leads to a large 2H enrichment (+425‰) in solutions. In the absence of hydrothermal water input containing H2S, we demonstrate that the relationship between δ18O and δ2H can be easily used in a way to trace the origin of the ClO3 and ClO4 in groundwater. Isotopes evidenced first a leakage from end-product storage tanks or during the production process itself. Then, an accumulation and release of ClO3 and ClO4 from soil is demonstrated. Our study successfully shows that stable isotopes are a powerful and low cost tool for tracing pollutant plumes in an industrial context using electrolysis process.

Characterization and mobility of arsenic and heavy metals in soils polluted by the destruction of arsenic-containing shells from the Great War.

Destruction of chemical munitions from World War I has caused extensive local top soil contamination by arsenic and heavy metals. The biogeochemical behavior of toxic elements is poorly documented in this type of environment. Four soils were sampled presenting different levels of contamination. The range of As concentrations in the samples was 1937-72,820mg/kg. Concentrations of Zn, Cu and Pb reached 90,190mg/kg, 9113mg/kg and 5777mg/kg, respectively. The high clay content of the subsoil and large amounts of charcoal from the use of firewood during the burning process constitute an ample reservoir of metals and As-binding materials. However, SEM-EDS observations showed different forms of association for metals and As. In metal-rich grains, several phases were identified: crystalline phases, where arsenate secondary minerals were detected, and an amorphous phase rich in Fe, Zn, Cu, and As. The secondary arsenate minerals, identified by XRD, were adamite and olivenite (zinc and copper arsenates, respectively) and two pharmacosiderites. The amorphous material was the principal carrier of As and metals in the central part of the site. This singular mineral assemblage probably resulted from the heat treatment of arsenic-containing shells. Microbial characterization included total cell counts, respiration, and determination of As(III)-oxidizing activities. Results showed the presence of microorganisms actively contributing to metabolism of carbon and arsenic, even in the most polluted soil, thereby influencing the fate of bioavailable As on the site. However, the mobility of As correlated mainly with the availability of iron sinks.

Investigations of natural attenuation in groundwater near a landfill and implications for landfill post-closure.

The controlled landfill technology is now adopting passive attenuation techniques as an increasing number of landfill sites reach the post-closure phase. During the post-closure phase, landfill operators need to convince environmental authorities that landfills no longer pose a threat to health or the environment. The demonstration of acceptable risk should rely in particular on data collected during environmental monitoring in addition to modelling of possible future evolutions of environmental concentrations. One difficulty that is typically encountered in France is related to the fact that groundwater monitoring systems around landfills are often insufficiently detailed to provide conclusive evidence of natural attenuation mechanisms. This paper presents data on groundwater quality in the vicinity of an old landfill located in a complex aquifer system. While isotopic data show a signature of the landfill leachate in the groundwater in the vicinity of the landfill, chemical analyses do not suggest a strong influence, which could be indicative of natural attenuation mechanisms in the groundwater. However, the complexity of the groundwater system in this area is such that it cannot be excluded that a pollutant flux is being overlooked. Implications of demonstrating natural attenuation during the landfill post-closure phase, with respect to groundwater monitoring, are discussed.