Sea spray as a secondary source of chlorinated persistent organic pollutants? - Conclusions from a comparison of seven fresh snowfall events in 2019 and 2021.

Secondary sources of persistent organic pollutants (POPs) gain in importance worldwide as primary sources decline. In this work, we aim to determine whether sea spray may be a secondary source of chlorinated POPs to the terrestrial Arctic, since a similar mechanism was proposed there only for the more water-soluble POPs. To this end, we have determined polychlorinated biphenyls and organochlorine pesticides concentrations in fresh snow and seawater collected in the vicinity of the Polish Polar Station in Hornsund in two sampling periods covering spring 2019 and 2021. To support our interpretations, we include also metal and metalloid, and stable hydrogen and oxygen isotopes analysis in those samples. A significant correlation was found between the concentrations of POPs and the distance from the sea at the sampling point, yet the confirmation of sea spray impact lies more in capturing an event with negligible long-range transport influence where the detected chlorinated POPs (Cl-POPs) matched in composition the compounds enriched in the sea surface microlayer, which is both a source of sea spray and a seawater microenvironment rich in hydrophobic substances.

Salt wedges and trapped brines of low-latitude endoreic saline lakes as potential modulators of GHG emission.

Large salt lakes are long-term witnesses to climatic conditions and land use in their basins. The majority are experiencing a drastic drop in water levels due to climate change and human impact. Endoreic Lake Urmia (NW Iran), the sixth largest salt lake worldwide, is a striking example of this decline. Quantification of the relative contributions of natural variability and human impact on the lake's water supply is therefore essential. Here we present isotopic and radiocarbon analyses of surface and groundwater from the Shahr Chay River catchment, entering Lake Urmia on its western shore, and radiocarbon dating of a sedimentary core. Lake Urmia behaves like a large saltwater wedge almost entirely fed by the river and shallow groundwater. This leads to trapping of residual brines and formation of CH4 and secondary CO2 greenhouse gases, impacting sediment geochemical records and corresponding time scales for paleoenvironmental reconstructions. We conclude that (1) salt lakes functioning like a saline wedge, allowing organic matter oxidation, could contribute to increasing methane sources or reducing carbon sinks globally, and (2) endoreic basins worldwide need to be monitored before aridification-related salinization leads to the establishment of a saline wedge precluding any possibility of return to an equilibrium state.

Elevated uranium concentration and low activity ratio (234U/238U) in the Œuf river as the result of groundwater-surface water interaction (Essonne river valley, South of Paris Basin, France).

Uranium (U) is a naturally occurring radioactive heavy metal widely distributed on Earth. Noticeable elevated U concentration and low activity ratio (AR) were occasionally detected in headwater stream of the Essonne river (Seine Basin, France), the namely Œuf river. This paper aims at providing new insight on geogenic U features in headwater streams and examines the role of river-groundwater interaction. The Œuf river was sampled four times in 2020 to investigate the influence of heterogeneous geology and hydrological seasonality. The dissolved fraction of water samples was analyzed for a variety of chemical parameters (anion, major, minor and trace element concentrations, isotopes 234U and 238U). The Œuf river was shown to exhibit elevated U concentration up to 19.3 µg L-1 (exceeding by 100-fold the value of 0.19 µg L-1 known for riverine average) and low AR down to 0.41 (almost the third of the value expected in surface water, i.e., 1.17). The Œuf river got enriched in U when receiving groundwater from Beauce Limestone Aquifer System. High U concentration (above 15 µg L-1) was found in association with low AR (below 0.5) in the stream water when flowing in the outcrop zone of one BLAS unit. Taking advantage of changes in the stream flow conditions and the geochemical contrast between surface and ground waters, mixing volumes were calculated. This study first examined the potential of using U isotopes in combination with selenium as hydrogeochemical tracers of the river-groundwater continuum. In HWS, the aquifer discharge was shown to supply 12 to 59 % of the river water. This study demonstrates the key role played by the river-groundwater interaction on river water chemistry in small streams draining catchment with various geology setting. It also supports the use of combining redox sensitive trace elements to track the river-groundwater continuum.

Transfer and degradation of the common pesticide atrazine through the unsaturated zone of the Chalk aquifer (Northern France).

Groundwater in the Chalk aquifer is an important water resource whose quality has degraded due to fertilizer and pesticide use. Atrazine, classified as a priority substance, has been one of the most applied pesticides and also one of the most frequently detected pesticides in groundwater. The present study investigated the transfer and degradation of atrazine in the unsaturated zone of the Chalk aquifer in Northern France. The study was conducted in an underground quarry (Saint-Martin-le-Noeud), which provides a direct access to the water table and intercepts the unsaturated zone at different depths. The lake and the ceiling percolation of 16 sites throughout the quarry were followed. For 16 sites, the percolating flow rate and lake level were measured and the lake water was sampled for nitrate, atrazine and deethylatrazine (DEA, main degradation product of atrazine) analysis over 2.5 years. High spatial variations in hydrodynamics (percolating flow rate and lake level) and in lake water quality (atrazine between 55±11 and 202±40 ng L-1 and DEA between 269±53 and 1727±345 ng L-1) indicate that the properties of the unsaturated zone influence the transfer and the degradation of atrazine. A counterclockwise hysteresis characterizes the relationship between the lake level and atrazine concentration. Temporal variation shows that the atrazine is transferred through the matrix and fractures with a delay caused by the sorption process that differs in atrazine and DEA. The layer of clay-with-flints is shown to favor the degradation of atrazine near the surface. Preferential pathways may be created below clay-with-flints, through which the transfer of atrazine is quicker.

Water, nitrate and atrazine transfer through the unsaturated zone of the Chalk aquifer in northern France.

The water quality of the Chalk aquifer is degrading due to fertilizers and pesticides use which are classified as toxic to public health. The study aims to provide a better understanding of the transfer processes in the unsaturated zone of the Chalk aquifer using different environmental tracers (nitrate, atrazine and tritium). The study was conducted in an underground quarry in northern France (St. Martin le Noeud). The quarry provides direct access to the lower part of the unsaturated zone of the Chalk at a depth of 18-30 m. Fifteen sites throughout the quarry display percolation directly from the unsaturated zone. Since percolation intensity is heterogeneous at one site, a comparison was made between the variation of geochemical properties of ten samples from one site and the spatial variation of samples from 15 sites throughout the quarry. Using the Siegel-Tukey and Wilcoxon tests, we found that the variation between the sites is higher than the variation within one site. Therefore, one percolation sample can be used to represent one site. The transfer time of nitrate and atrazine is estimated based on its use in the cultivated fields. Pore water with no contamination indicates water infiltrated before the use of contaminants at the surface, and pore water with a high concentration of contaminants indicates water infiltrated during the use of contaminants at the surface. The transfer time of water molecules is estimated using the time series of tritium. Transfer velocities were computed for each environmental tracer (nitrate, atrazine and tritium) by dividing the estimated transfer time by the depth of each site. Two transfer velocity ranges are determined: (1) <0.32 ±â€¯0.02 m/year and (2) between 0.72 ±â€¯0.14 and 2.15 ±â€¯0.43 m/year, showing most water transfer through the matrix but also a mixture of water with different velocities.

Estimate of recharge of a rising water table in semiarid Niger from 3H and 14C modeling.

A hydrodynamic survey carried out in semiarid southwest Niger revealed an increase in the unconfined ground water reserves of approximately 10% over the last 50 years due to the clearing of native vegetation. Isotopic samplings (3H, 18O, 2H for water and 14C, 13C for the dissolved inorganic carbon) were performed on about 3500 km2 of this silty aquifer to characterize recharge. Stable isotope analyses confirmed the indirect recharge process that had already been shown by hydrodynamic surveys and suggested the tracers are exclusively of atmospheric origin. An analytical model that takes into account the long-term rise in the water table was used to interpret 3H and 14C contents in ground water. The natural, preclearing median annual renewal rate (i.e., recharge as a fraction of the saturated aquifer volume) lies between 0.04% and 0.06%. For representative characteristics of the aquifer (30 m of saturated thickness, porosity between 10% and 25%), this implies a recharge of between 1 and 5 mm/year, which is much lower than the estimates of 20 to 50 mm/year for recent years, obtained using hydrological and hydrodynamic methods and the same aquifer parameters. Our study, therefore, reveals that land clearing in semiarid Niger increased ground water recharge by about one order of magnitude.