Groundwater arsenic biogeochemistry-Key questions and use of tracers to understand arsenic-prone groundwater systems

Over 100,000,000 people worldwide are exposed to high arsenic groundwater utilised for drinking or cooking.The consequent global avoidable disease burden is estimated to be of the order of 100,000 avoidable deaths or more per annum from just direct exposures — i.e.excluding indirect exposure(from rice and other foods)and excluding morbidity.Notwithstanding 1000 s of papers published on arsenic(hydro)(bio)geochemistry,there remain a number of key outstanding questions to be addressed in relation to arsenic geoscience-these include questions related to:(i)the role of human activities —irrigation,agriculture and other land uses — on arsenic mobilisation in groundwaters;(ii)the specific sources,nature and role of organics,minerals and microbial communities involved in arsenic mobilisation;(iii)the relationship to microscopic to macroscopic scale geological(including tectonic)and evolution processes;(iv)unravelling the over-printing of multiple processes in complex highly heterogeneous aquifer systems and(v)using increasing understanding of the controls of arsenic mobility in groundwaters systems to informing improved locally-relevant remediation and mitigation approaches.This article further summarises how the 9 further papers in this Special Issue address some of these questions through the use of chemical and/or isotopic tracers.     

The timing and extent of the eruption of the Siberian Traps large igneous province: Implications for the end-Permian environmental crisis

We present new high-precision ⁴⁰Ar/³⁹Ar ages on feldspar and biotite separates to establish the age, duration and extent of the larger Siberian Traps volcanic province. Samples include basalts and gabbros from Noril'sk, the Lower Tunguska area on the Siberian craton, the Taimyr Peninsula, the Kuznetsk Basin, Vorkuta in the Polar Urals, and from Chelyabinsk in the southern Urals. Most of the ages, except for those from Chelyabinsk, are indistinguishable from those found at Noril'sk. Cessation of activity at Noril'sk is constrained by a ⁴⁰Ar/³⁹Ar age of 250.3 ± 1.1 Ma for the uppermost Kumginsky Suite.The new ⁴⁰Ar/³⁹Ar data confirm that the bulk of Siberian volcanism occurred at 250 Ma during a period of less than 2 Ma, extending over an area of up to 5 million km². The resolution of the data allows us to confidently conclude that the main stage of volcanism either immediately predates, or is synchronous with, the end-Permian mass extinction, further strengthening an association between volcanism and the end-Permian crisis. A sanidine age of 249.25 ± 0.14 Ma from Bed 28 tuff at the global section and stratotype at Meishan, China, allows us to bracket the P–Tr boundary to 0.58 ± 0.21 myr, and enables a direct comparison between the ⁴⁰Ar/³⁹Ar age of the Traps and the Permo–Triassic boundary section.Younger ages (243 Ma) obtained for basalts from Chelyabinsk indicate that volcanism in at least the southern part of the province continued into the Triassic.     

Evaluating different GCMs for predicting spatial recharge in an irrigated arid region

Groundwater systems in arid regions will be particularly sensitive to climate change owing to the strong dependence of rates of evapotranspiration on temperature, and shifts in the precipitation regimes. Irrigation use in these arid regions is typically a large component of the water budget, and may increase due to changes in soil moisture resulting from higher temperatures and changes in the timing of precipitation events. In this study, future predicted climate change scenarios from three global climate models (CGCM1 GHG+A1, CGCM3.1 A2, and HadCM3 A2) are used to determine the sensitivity of recharge to different climate models in an irrigated agricultural region. The arid Oliver region (annual precipitation 300 mm) in the Okanagan Basin, British Columbia, is used to demonstrate the approach. Irrigation return flow, as a contribution to total diffuse recharge, is simulated by calculating the daily applied irrigation based on estimates of seasonal crop water demand and the forecasted precipitation and evaporation data. The relative contribution of irrigation return flow to groundwater recharge under current and future climate conditions is modelled. Temperature data were downscaled using Statistical Downscaling Model (SDSM), while precipitation and solar radiation changes were estimated directly from the GCM data. Shifts in climate, from present to future predicted, were applied to a stochastic weather generator, and used to force a one-dimensional hydrologic model, HELP 3.80D. Results were applied spatially, according to different soil profiles, slope and vegetation, over a 22.5 km by 8.6 km region. Changes to recharge in future time periods for each GCM result in modest increases of recharge with the peak recharge shifting from March to February. Lower recharge rates and higher potential evapotranspiration rates are similarly predicted by all three models for the summer months. All scenarios show that the potential growing season will expand between 3 and 4 weeks due to increases in temperature. However, the magnitude of the change varies considerably between models. CGCM3.1 has the largest increases of recharge rates, CGCM1 has very minor increases, and HadCM3 is relatively stable (as indicated by the near-zero changes between climate states). The significant differences between these three models indicate that prediction of future recharge is highly dependent on the model selected. The minor increase of annual recharge in future predicted climate states is due the shift of peak recharge from increased temperature. Irrigation rates dominate total recharge during the summer months in this arid area. Recharge in irrigated areas is significantly higher than natural recharge, with irrigation return flow between 25% and 58%. A comparison of recharge results for the least efficient and the most efficient irrigation systems indicates that the latter are more sensitive to choice of GCM.     

The partitioning of Triclosan between aqueous and particulate bound phases in the Hudson River Estuary

The distribution of Triclosan within the Hudson River Estuary can be explained by a balance among the overall effluent inputs from municipal sewage treatment facilities, dilution of Triclosan concentrations in the water column with freshwater and seawater inputs, removal of Triclosan from the water column by adsorption to particles, and loss to photodegradation. This study shows that an average water column concentration of 3 ± 2 ng/l (in the lower Hudson River Estuary) is consistent with an estimate for dilution of average wastewater concentrations with seawater and calculated rates of adsorption of Triclosan to particles. An average Triclosan sediment concentration of 26 ± 11 ng/g would be in equilibrium with the overlying water column if Triclosan has a particle-to-water partitioning coefficient of k_d  10⁴, consistent with laboratory estimates.     

Characterization of a mud deposit offshore of the Patos Lagoon,southern Brazil

Rapid deposition of mud on the beach along the shoreface of Rio Grande do Sul, Brazil dramatically influences the normal operations in the littoral zone. In the surf zone, fluid and suspended mud opposes water-wave movement and dissipates water-wave energy; on the beach, mud limits trafficability. As part of a multinational, multidisciplinary program to evaluate the influence of mud strength, density and viscosity on water-wave attenuation, sediments were evaluated in situ or collected for evaluation from an area offshore of Cassino Beach, slightly south of the Patos Lagoon mouth. Shear strength of deposited sediments ranged from 0.6 kPa at the seafloor to 3.4 kPa at ∼1 m below the seafloor. Mud sediments were also collected to simulate the in situ response of fluid mud to shear stresses. For this determination, rheological evaluations were made using a strain-controlled Couette viscometer on numerous remixed samples that ranged in density from 1.05 to 1.30 g/cm³. It was determined that this mud is a non-ideal Bingham material in that it has a true initial yield stress as well as a upper Bingham yield stress. Initial yield stress ranged from 0.59 to 2.62 Pa, upper Bingham yield stress ranged from 1.05 to 7.6 Pa. Apparent viscosity ranged from 0.02 to 4.7 Pa s with the highest viscosities occurring between the two yield stresses. Sediment strength in the remixed samples is 2 to 3 orders of magnitude lower than the horizontal shear strength of the sediment bed as determined by shear vane or predicted from penetrometer measurements. This difference is partially due to the fact that rheological evaluations are made on fully remixed sediments, whereas horizontal shear strength is determined within relatively undisturbed sediments. Similar values of viscosity and shear strength are comparable to those determined for mud in other coastal areas where fluid mud deposits occur.     

Diel cycles of hydrogen peroxide in marine bathing waters in Southern California, USA: In situ surf zone measurements

Hydrogen peroxide is photochemically produced in natural waters. It has been implicated in the oxidative-induced mortality of fecal indicator bacteria (FIB), a microbial water quality measure. To assess levels and cycling of peroxide in beach waters monitored for FIB, diel studies were carried out in surf zone waters in July 2009 at Crystal Cove State Beach, Southern California, USA. Maximum concentrations of 160–200 nM were obtained within 1 h of solar noon. Levels dropped at night to 20–40 nM, consistent with photochemical production from sunlight. Day-time production and night-time dark loss rates averaged 16 ± 3 nM h⁻¹ and 12 ± 4 nM h⁻¹ respectively. Apparent quantum yields averaged 0.07 ± 0.02. Production was largely dominated by sunlight, with some dependence on chromophoric dissolved organic matter (CDOM) levels in waters with high absorption coefficients. Peroxide levels measured here are sufficient to cause oxidative-stress-induced mortality of bacteria, affect FIB diel cycling and impact microbial water quality in marine bathing waters.     

The COPAS’08 expedition to the Patagonian Shelf: Physical and environmental conditions during the 2008 coccolithophore bloom

Here we present observations of the hydrography of the Patagonian Shelf, shelf break and offshore waters, with reference to the environmental conditions present during the period of peak coccolithophore abundance. Analysis of a hydrographic dataset collected in December 2008 (austral spring/summer), as part of the Coccolithophores of the Patagonian Shelf (COPAS) research cruise, identified 5 distinct surface water masses in the region between 37°S and 55°S. These water masses, identified through salinity gradients, displayed varying mixed layer depths, macronutrient inventories and chlorophyll-a fluorescence. Subantarctic Shelf Water (SSW), located to the north of the Falkland Islands and extending north along the shelf break, was also host to a large coccolithophore bloom. The similarities between the distribution of calcite, as seen in remote sensing data, and SSW indicate that the coccolithophore bloom encountered conditions conducive to bloom development within this water mass. Analysis of chemical and environmental data also collected during the COPAS cruise revealed that many of the commonly cited conditions for coccolithophore bloom development were present within SSW (e.g. low N:P ratio, high N:Si ratio, shallow mixed layer depth). In the other water masses present on the Patagonian Shelf greater variability in these same parameters may explain the more diffuse concentration of calcite, and the smaller size of possible coccolithophore blooms. The distribution of SSW is strongly influenced by the latitudinal variation in shelf break frontal width, which varies from 20 to 200 km, and consequently strong hydrographic controls underlie the position of the coccolithophore bloom during austral summer.     

Test of rock physics models for prediction of seismic velocities in shallow unconsolidated sands: a well log data case‡

This paper tests the ability of various rock physics models to predict seismic velocities in shallow unconsolidated sands by comparing the estimates to P and S sonic logs collected in a shallow sand layer and ultrasonic laboratory data of an unconsolidated sand sample. The model fits are also evaluated with respect to the conventional model for unconsolidated sand. Our main approach is to use Hertz‐Mindlin and Walton contact theories, assuming different weight fractions of smooth and rough contact behaviours, to predict the elastic properties of the high porosity point. Using either the Hertz‐Mindlin or Walton theories with rough contact behaviour to define the high porosity endpoint gives an over‐prediction of the velocities. The P‐velocity is overpredicted by a factor of ～1.5 and the S‐velocity by a factor of ～1.8 for highly porous gas‐sand. The degree of misprediction decreases with increasing water saturation and porosity.Using the Hertz‐Mindlin theory with smooth contact behaviour or weighted Walton models gives a better fit to the data, although the data are best described using the Walton smooth model. To predict the properties at the lower porosities, the choice of bounding model attached to the Walton Smooth model controls the degree of fit to the data, where the Reuss bound best captures the porosity variations of dry and wet sands in this case since they are caused by depositional differences. The empirical models based on lab experiments on unconsolidated sand also fit the velocity data measured by sonic logs in situ, which gives improved confidence in using lab‐derived results.     

Nekton Use of Flooded Salt Marsh and an Assessment of Intertidal Creek Pools as Low-Tide Refuges

Patterns of nekton occurrence on the salt marsh surface at high tide and in an adjacent intertidal creek pool at low tide were used to investigate movements of nekton in an intertidal basin. Paired collections were made in North Inlet estuary, SC on 67 dates over 9 years. Comparisons of high- and low-tide total abundance indicated that what remained in the creek pool at low tide was representative of the nekton on the flooded marsh. Of the 64 taxa collected, the same 8 species ranked in the top 10 in both the high- and low-tide collections. Abundances of most resident species were positively correlated with the area of marsh flooded, but mummichog (Fundulus heteroclitus), the most abundant resident, was not. Abundances of young-of-the-year transient species were not related to the extent of tidal flooding. Some transient species used the flooded marsh but did not occupy the pool at low tide, and others found in the pool did not use the marsh. Differences in abundance, biomass, and length between the marsh and pool collections indicated differences in the tendency of species and life stages to retreat downstream of the pool to the subtidal channel. Proportionately more of the nekton that were present on the flooded marsh left the intertidal basin when large changes in temperature and salinity occurred between high and low tides. More transients left the basin following higher tides, but more residents did not. The results demonstrate a wide range of taxonomic and ontogenetic patterns among nekton using intertidal salt marsh basins and the underappreciated importance of intertidal creek pools as alternative low-tide refuges.     

Virus occurrence in private and public wells in a fractured dolostone aquifer in Canada

Groundwater samples from 22 wells completed in a regional fractured dolostone aquifer in the Guelph region of southern Ontario, Canada, were collected over an 8-month period and analyzed for viruses and Campylobacter jejuni. Only 8% of the 118 samples exhibited viruses at extremely low concentrations, but of the 22 wells sampled, 10 (45%) were positive for human enteric viruses (polyomavirus, adenovirus A, and GII norovirus) including 5 of the 8 public supply wells (62.5%) and 5 of the 11 private wells (45%). Each virus-positive well had only one virus occurrence with six sampling events during the 8-month sampling campaign and only one virus type was detected in each well. The probability of virus detection was positively associated with well open-interval length. Virus concentration (in the wells that were virus-positive) was negatively associated with well depth and open-interval length and positively associated with overburden thickness (i.e., the thickness of unconsolidated materials overlying bedrock facies) and the amount of precipitation 8–14 and 15–21 days prior to the sampling date. The ephemeral nature of the virus detections and the low detection rate on a per sample basis were consistent with previous studies. The percentage of virus-positive wells, however, was much higher than previous studies, but consistent with the fact that the hydrogeologic conditions of fractured bedrock aquifers create wide capture zones and short groundwater travel times to wells making them more vulnerable to contamination occurrence but at very low concentrations.