Geochemical determination of the fate and transport of injected fresh wastewater to a deep saline aquifer

Deep well injection into non-potable saline aquifers of treated domestic wastewater has been used in Florida for decades as a safe and effective alternative to ocean outfall disposal. The objectives of this study were to determine the fate and transport of injected wastewater at two deep well injection sites in Miami Dade County, Florida, USA. Detection of ammonium in the Middle Confining units of the Floridan aquifer above the injection zone at both sites has been interpreted as evidence of upward migration of injected wastewater, posing a risk to underground sources of drinking water. Historical water quality data, including ammonia, chloride, temperature, and pH from existing monitoring wells at both sites from 1983 to 2008, major ions collected monthly from 2006 and 2008, and a synoptic sampling event for stable isotopes, tritium, and dissolved gases in 2008, were used to determine the source of ammonium in groundwater and possible migration pathways. Geochemical modeling was used to determine possible effects of injected wastewater on native water and aquifer matrix geochemistry. Injected wastewater was determined to be the source of elevated ammonium concentrations above ambient water levels, based on the results of major ion concentrations, tritium, dissolved noble gases and 15N isotopes analyses. Various possible fluid migration pathways were identified at the sites. Data for the south site suggest buoyancy-driven vertical pathways to overlying aquifers bypassing the confining units, with little mixing of injected wastewater with native water as it migrated upward. Once it is introduced into an aquifer, the injectate appeared to migrate advectively with the regional groundwater flow. Geochemical modeling indicated that CO 2-enriched injected wastewater allowed for carbonate dissolution along the vertical pathways, enhancing permeability along these flowpaths. At the north site, diffusive upward flow through the confining units or offsite vertical pathways were determined to be possible, however no evidence was detected for any on-site confining unit bypass pathway. No evidence was observed at either site of injected wastewater migration to the Upper Floridan aquifer, which is used as a municipal water supply and for aquifer storage and recovery.

Stable-isotope ratios and accumulation rates of four firn cores from the Dronning Maud Land, Antarctica

Four firn cores were retrieved in 2007 at two ridges in the area of the Ekström Ice Shelf, Dronning Maud Land, coastal East Antarctica, in order to investigate the recent regional climate variability and the potential for future extraction of an intermediate-depth core. Stable water-isotope analysis, tritium content and electrical conductivity were used to date the cores. For the period 1981-2006 a strong and significant correlation between the stable-isotope composition of firn cores in the hinterland and mean monthly air temperatures at Neumayer station was (r=0.54-0.71). No atmospheric warming or cooling trend is inferred from our stable-isotope data for the period 1962-2006. The stable-isotope record of the ice/firn cores could expand well beyond the meteorological record of the region. No significant temporal variation of accumulation rates was detected. However, decreasing accumulation rates were found from coast to hinterland, as well as from east (Halvfarryggen) to west (Søråsen). The deuterium excess (d) exhibits similar differences (higher d at Søråsen, lower d at Halvfarryggen), with a weak negative temporal trend on Halvfarryggen (0.04 per mil/a), probably implying increasing oceanic input. We conclude that Halvfarryggen acts as a natural barrier for moisture-carrying air masses circulating in the region from east to west.

(Table 1) Helium isotope ratios of sediment core TT013_114

We present a helium isotope record for core TT013-114PC from the central equatorial Pacific (140°W, 4°N, 4432 m water depth) spanning a period of 1 million years. We focus on the time interval from 560 to 800 kyr, largely coinciding with the mid-Pleistocene climate transition (MPT) when the dominant period of the Earth's climate variability shifted from 41 kyr to 100 kyr. The terrigenous 4He concentrations from our study correlate very well with published titanium concentrations in this core strongly supporting the use of terrigenous 4He as a monitor of continental dust. Normalizing titanium and terrigenous 4He concentrations to 3He suggests that the dust supply during the MPT was approximately 30% lower compared to the subsequent period (560-100 kyr). The 3He-normalized barium, aluminum and phosphorus concentrations, trace elements with a predominantly biogenic source in these sediments, are relatively constant. This is in contrast to previous studies that reported an apparent rise of titanium-normalized productivity proxies. Rather than a significant increase in productivity during the MPT, we conclude that the dust flux to the central equatorial Pacific was reduced and that the export productivity was approximately constant during this period of climate reorganization.

Talos Dome Ice Core Deuterium Data

During the 1996 Programma Nazionale di Ricerche in Antartide-International Trans-Antarctic Scientific Expedition traverse, two firn cores were retrieved from the Talos Dome area (East Antarctica) at elevations of 2316 m (TD, 89 m long) and 2246 m (ST556, 19 m long). Cores were dated by using seasonal variations in non-sea-salt (nss) SO42- concentrations coupled with the recognition of tritium marker level (1965-1966) and nss SO42- spikes due to the most important volcanic events in the past (Pinatubo 1991, Agung 1963, Krakatoa 1883, Tambora 1815, Kuwae 1452, Unknown 1259). The number of annual layers recognized in the TD and ST556 cores was 779 and 97, respectively. The dD record obtained from the TD core has been compared with other East Antarctic isotope ice core records (Dome C EPICA, South Pole, Taylor Dome). These records suggest cooler climate conditions between the middle of 16th and the beginning of 19th centuries, which might be related to the Little Ice Age (LIA) cold period. Because of the high degree of geographical variability, the strongest LIA cooling was not temporally synchronous over East Antarctica, and the analyzed records do not provide a coherent picture for East Antarctica. The accumulation rate record presented for the TD core shows a decrease during part of the LIA followed by an increment of about 11% in accumulation during the 20th century. At the ST556 site, the accumulation rate observed during the 20th century was quite stable.

(Table 1) Water chemistry of groundwater and snow samples from three sites in Ontario, Canada

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently ''natural'' ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path. Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.

Profesionales de la educación en la Hispania romana

La epigrafía latina nos ha legado el recuerdo de doce docentes y un grupo de maestros de escuela en Hispania. Los diferentes textos, la mayoría de carácter funerario y procedente del ámbito urbano, nos aportan información acerca de las funciones que estos profesionales desempeñaron en la sociedad hispana, así como del contexto socio-jurídico del que provenían. En este sentido, la pieza más valiosa es la inscripción dedicada a un gramático llamado L. Memmius Probus en la antigua Tritium Magallum, gracias a la cual conocemos las circunstancias concretas en las que trabajó este educador.

Isotope characterisation of deep aquifers in the Gwda catchment, northern Poland

We present the results of isotope measurements (δ 18 O, δ D, δ 13 C DIC and 14 C) and chemical analyses (TDS, TOC, HCO 3– , SO 42– , Cl – , NO 3– , NH 4+ , Ca 2+ , Mg 2+ Na + and K + ) conducted on groundwater samples collected from deep Cenozoic aqui- fers. These aquifers are the basic source of drinking water at numerous localities within the study area in northern Po- land. Most of the δ 18 O determinations are characterised by low variability (i.e., > 70 per cent of δ 18 O are between –9.5‰ and –9.2‰). In most cases tritium activity was not detected or its content slightly exceeded the uncertainty of measure- ment (from ±0.3 T.U. to ± 0.5 T.U.). On average, 14 C activity is twice higher than that under similar conditions and in hydrogeological systems. The δ 13 C DIC values fall within the –13.6‰ to –12.8‰ range. A slight variability is observed when considering all isotope and chemical data within the study area and under these hydrogeological conditions. In general, the results of isotope and chemical analyses seem to be homogeneous, indicating the presence of closely similar groundwaters in the system, irrespective of geological formation. It is likely that there is a significant hydraulic connec- tion between shallow and deep aquifers in the Gwda catchment, which indicates the potential for seepage of pollutants from shallow Pleistocene to deep Miocene aquifers. This can endanger the latter by e.g., high concentrations of NO 3– , SO 42– and Cl – ions from shallow aquifers within the Gwda catchment.

Shallow Groundwater Quality and Geochemistry in the Shields River Basin, South-Central Montana

Water samples were collected from 33 domestic wells, 2 springs, and 3 streams in the Shields River Basin (Basin) in southwest Montana. Samples were collected in 2013 to describe the chemical quality of groundwater in the Basin. Sampling was done to assess potential impacts to water quality from recent exploratory oil and gas drilling and to establish baseline water quality conditions. Wells were selected in areas near and away from oil and gas drilling and in areas susceptible to contamination. Water samples from surface water sites were collected in October to characterize base flow conditions. Physical characteristics of the land surface, soils, and shallow aquifers were used to assess groundwater susceptibility to contamination from the land surface. This analysis was completed using GIS. Samples were analyzed for major ions, trace metals, water isotopes of oxygen and hydrogen. A subset (24) of samples were analyzed for tritium and organic constituents (GRO, DRO, BTEX, methane, ethylene, and ethane). One sample exceeded the human health drinking water standard for selenium. Dissolved methane and ethylene gas were detected in six samples at concentrations less than 0.184 milligrams per liter. Three locations were resampled in 2014, and no methane or ethylene was detected. Shallow groundwater and streams are generally calcium- or sodium-bicarbonate type water with total dissolved solids concentration less than 300 milligrams per liter. Some wells produce either sodium-chloride or sodium-sulfate type water suggesting slower flow paths and more rock-water interaction. Tritium concentrations suggest that older water (TU< 0.8), recharged prior to the mid-1950’s, is generally sodium type, whereas younger water (TU > 4) is generally a calcium type. Water-quality data from this study were compared to available historic data in the Basin. Additionally, the USGS Produced Waters Geochemical database was queried for chemical data of produced waters from reservoir rocks throughout Montana and the surrounding states. Comparisons to historic and produced water chemical data suggest no impact to shallow groundwater quality from exploratory oil and gas drilling.

2013 survey of Iowa groundwater and evaluation of public well vulnerability classifications for contaminants of emerging concern (2015)

Studies in Iowa have long documented the vulnerability of wells with less than 50 feet (15 meters) of confining materials above the source aquifer to contamination from nitrate and various pesticides. Recent studies in Wisconsin have documented the occurrence of viruses in untreated groundwater, even in wells considered to have little vulnerability to contamination from near-surface activities. In addition, sensitive methods have become available for analyses of pharmaceuticals and pesticides. This study represents the first comprehensive examination of contaminants of emerging concern in Iowa’s groundwater conducted to date, and one of the first conducted in the United States. Raw groundwater samples were collected from 66 public supply wells during the spring of 2013, when the state was recovering from drought conditions. Samples were analyzed for 206 chemical and biological parameters; including 20 general water-quality parameters and major ions, 19 metals, 5 nutrients, 10 virus groups, 3 species of pathogenic bacteria, 5 microbial indicators, 108 pharmaceuticals, 35 pesticides and pesticide degradates, and tritium. The wells chosen for this study represent a diverse range of ages, depths, confining material thicknesses, pumping rates, and land use settings. The most commonly detected contaminant group was pesticide compounds, which were present in 41% of the samples. As many as 6 pesticide compounds were found together in a sample, most of which were chloroacetanilide degradates. While none of the measured concentrations of pesticide compounds exceeded current benchmark levels, several of these compounds are listed on the U.S. Environmental Protection Agency’s Contaminant Candidate List and could be subject to drinking water standards in the future. Despite heavy use in the past decade, glyphosate was not detected, and its metabolite, aminomethylphosphonic acid, was only detected in two of 60 wells tested (3%) at the detection limit of 0.02 μg/L. Pharmaceutical compounds were detected in 35% of 63 samples. Of the 14 pharmaceuticals detected, six had reported concentrations above the method reporting limit, with the maximum reported concentration of 826 ng/L for acetaminophen. Diphenhydramine was the only pharmaceutical to have two detections above the reporting limit, at 24.5 and 145 ng/L. Eight pharmaceuticals had confirmed detections at concentrations below the method reporting limit. Caffeine was the most frequently detected pharmaceutical compound (25%), followed by the caffeine metabolite, 1,7-dimethylxanthine (16%). Microorganisms were detected in 21% of the wells using quantitative polymerase chain reaction methodologies. The most frequently detected microorganism was the pepper mild mottle virus (PMMV), a plant pathogen found in human waste. PMMV was detected in 17% of samples at concentrations ranging from 0.4 to 6.38 gene copies per liter. GII norovirus, human polyomavirus, bovine polyomavirus, and Campylobacter were also detected, while adenovirus, enterovirus, GI norovirus, swine hepatitis E, Salmonella, and enterohemmorhagic E. coli were not detected. No correlations were found between viruses or pathogenic bacteria and microbial indicators. Wells with less than 50 feet (15 meters) of confining material were shown to have greater incidence of surface-related contaminants; however, significant relationships (p<0.05) between confining layer thickness and contaminants were only found for nitrate and herbicides.