Cl,N, C isotopic analysis of common agro-chemicals for identifying non-point source agricultural contaminants

The isotopic compositions of commercially available herbicides were analyzed to determine their respective ¹⁵N, ¹³C and ³⁷Cl signatures for the purposes of developing a discrete tool for tracing and identifying non-point source contaminants in agricultural watersheds. Findings demonstrate that of the agrochemicals evaluated, chlorine stable isotopes signatures range between δ³⁷Cl = −4.55‰ and +3.40‰, whereas most naturally occurring chlorine stable isotopes signatures, including those of road salt, sewage sludge and fertilizers, vary in a narrow range about the Standard Mean Ocean Chloride (SMOC) between −2.00‰ and +1.00‰. Nitrogen stable isotope values varied widely from δ¹⁵N = −10.86‰ to +1.44‰ and carbon stable isotope analysis gave an observed range between δ¹³C = −37.13‰ and −21.35‰ for the entire suite of agro-chemicals analyzed. When nitrogen, carbon and chlorine stable isotope analyses were compared in a cross-correlation analysis, statistically independent isotopic signatures exist suggesting a new potential tracer tool for identifying herbicides in the environment.     

Salt Waters of the Northern Apennine Foredeep Basin (Italy): Origin and Evolution

The salt waters from the Emilia-Romagna sector of the Northern Apennine Foredeep have been investigated using major and trace element and stable isotope (δ²H, δ¹⁸O, δ³⁷Cl, δ⁸¹Br and ⁸⁷Sr/⁸⁶Sr ratio). Ca, Mg, Na, K, Sr, Li, B, I, Br and SO₄ vs. Cl diagrams suggest the subaerial evaporation of seawater beyond gypsum and before halite precipitation as primary process to explain the brine’s salinity, whereas saline to brackish waters were formed by mixing of evaporated seawater and water of meteoric origin. A diagenetic end-member may be a third component for mud volcanoes and some brackish waters. Salinization by dissolution of (Triassic) evaporites has been detected only in samples from the Tuscan side of the Apennines and/or interacting with the Tuscan Nappe. In comparison with the seawater evaporation path, Ca–Sr enrichment and Na–K–Mg depletion of the foredeep waters reveal the presence of secondary processes such as dolomitization–chloritization, zeolitization–albitization and illitization. Sulfate concentration, formerly buffered by gypsum-anhydrite deposition, is heavily lowered by bacterial and locally by thermochemical reduction during burial diagenesis. From an isotopic point of view, data of the water molecule confirm mixing between seawater and meteoric end-members. Local ¹⁸O-shift up to +11‰ at Salsomaggiore is related to water–rock interaction at high temperature (≈150°C) as confirmed by chemical (Mg, Li, Ca distribution) and isotopic (SO₄–H₂O) geothermometers. ³⁷Cl/³⁵Cl and ⁸¹Br/⁷⁹Br ratios corroborate the marine origin of the brines and evidence the diffusion of halogens from the deepest and most saline aquifers toward the surface. The ⁸⁷Sr/⁸⁶Sr ratio suggests a Miocene origin of Sr and rule out the hypothesis of a Triassic provenance of the dissolved components for the analyzed waters issuing from the Emilia-Romagna sector of the foredeep. Waters issuing from the Tuscan side of the Apennines and from the Marche sector of the foredeep show higher ⁸⁷Sr/⁸⁶Sr ratios because of the interaction with siliciclastic rocks.     

Isotopically Enriched Geogenic δ81Br and δ37Cl: Primary Evidence for the Ascending Brine Model

Mass balance calculations and hydrodynamics of groundwater flow suggest that the solutes in brines of the coastal sabkha aquifer from the Emirate of Abu Dhabi are derived largely from ascending geologic brines into the sabkha from the underlying formations. Solute interpretation for the ascending brine model (ABM) was based on two independent but secondary lines of evidence (solute ratios and solute fluxes). In the current study, direct primary evidence for this ABM was provided through analyses of δ⁸¹Br, δ³⁷Cl, and ⁸⁷Sr/⁸⁶Sr. Different solute histories of geologic brine and sea water provide an “isotopic fingerprint” that can uniquely distinguish between the two possible sources. Samples from the coastal sabkha aquifer of Abu Dhabi were determined to have a mean δ⁸¹Br of 1.17‰ that is statistically equal, at the 95% confidence level, to the mean of 1.11‰ observed in the underlying geologic brine and statistically different than sea water. Similarly, the δ³⁷Cl in sabkha brine has a mean of 0.25‰ and is statistically equal to a mean of 0.21‰ in the underlying geologic brines at the 95% confidence level and statistically different from sea water. Also, dissolved strontium isotope data are consistent with the ABM and even with the complex set of processes in the sabkha, the variance in strontium isotope results is similar to the geologic brine. These observations provide primary direct evidence consistent that the major source of these solutes (and presumably others in the aquifer) is from discharging geologic brines, not from adjacent sea water.     

Geochemistry and stable isotopic signatures,including chlorine and bromine isotopes,of the deep groundwaters of the Siberian Platform,Russia

The chemical composition and the isotopic characteristics of formation waters from the Siberian Platform are presented. The study involved samples of formation brines from depths ranging from 100 to ∼4000 m at five different sites covering a large area of the Siberian Platform. Four water types were identified. The two main water types that were found are: (1) Ca–Cl brines that are believed to be the residual of an evaporated paleoseawater; and (2) Na–Cl brines that are derived mainly from halite dissolution. The origin of a third group of highly saline samples was not determined. However, the chemical and isotopic characteristics of this group of samples suggest that they were produced by various complex scenarios such as metamorphism, water–rock interaction, permafrost freezing and mixing. The last group of samples represents fresh and brackish waters across the area.     

Chemical evolution of an inland sabkha: a case study from Sabkha Matti,Saudi Arabia

Hydrogeology Journal - Sabkha Matti is a potential discharge point for regional groundwater systems in the Rub’ al Khali topographic basin of Saudi Arabia. The hydrogeochemical evolution of...