A. van Geen

A 120-yr record of widespread contamination from mining of the Iberian pyrite belt

A metal-enriched seawater plume entering the western Mediterranean Sea through the Strait of Gibraltar originates 300 km to the west in the Rio Tinto estuary of southwestern Spain. Mining of Rio Tinto ore, one of the largest metal-rich sulfide deposits in the world, started well before Roman times. Contemporary Rio Tinto waters draining the region are highly acidic (pH 2.5) with dissolved cadmium, zinc, and copper concentrations 10 5 ‐10 6 times higher than in uncontaminated surface water of the Gulf of Cadiz. Two dated sediment cores from the Spanish continental shelf show that metal inputs to the region increased with the onset of intensive mining activities during the second half of the 19th century. Although the impact of mining may have decreased over the past few decades, the Tinto river and estuary remain highly contaminated.

Enhanced marine productivity off western North America during warm climate intervals of the past 52 k.y

Studies of the Santa Barbara Basin off the coast of California have linked changes in its bottom-water oxygen content to millennial-scale climate changes as recorded by the oxygen isotope composition of Greenland ice. Through the use of detailed records from a sediment core collected off the Magdalena Margin of Baja California, Mexico, we demonstrate that this teleconnection predominantly arose from changes in marine productivity, rather than changes in ventilation of the North Pacific, as was originally proposed.

Arsenic migration to deep groundwater in Bangladesh influenced by adsorption and water demand

Drinking shallow groundwater with naturally elevated concentrations of arsenic is causing widespread disease in many parts of South and Southeast Asia. In the Bengal Basin, growing reliance on deep (>150 m) groundwater has lowered exposure. In the most affected districts of Bangladesh, shallow groundwater concentrations average 100 to 370 μg L−1, while deep groundwater is typically < 10 μg L−1. Groundwater flow simulations have suggested that, even when deep pumping is restricted to domestic use, deep groundwater in some areas of the Bengal Basin is at risk of contamination. However, these simulations have neglected the impedance of As migration by adsorption to aquifer sediments. Here we quantify for the first time As sorption on deeper sediments in situ by replicating the intrusion of shallow groundwater through injection of 1,000 L of deep groundwater modified with 200 μg L−1 of As into a deeper aquifer. Arsenic concentrations in the injected water were reduced by 70% due to adsorption within a single day. Basin-scale modelling indicates that while As adsorption extends the sustainable use of deep groundwater, some areas remain vulnerable; these areas can be prioritized for management and monitoring.

Ventilation changes in the northeast Pacific during the last deglaciation

Under present climate conditions, convection at high latitudes of the North Pacific is restricted to shallower depths than in the North Atlantic. To what extent this asymmetry between the two ocean basins was maintained over the past 20 kyr is poorly known because there are few unambiguous proxy records of ventilation from the North Pacific. We present new data for two sediment cores from the California margin at 800 and 1600 m depth to argue that the depth of ventilation shifted repeatedly in the northeast Pacific over the course of deglaciation. The evidence includes benthic foraminiferal Cd/Ca, 18O/16O, and 13C/12C data as well as radiocarbon age differences between benthic and planktonic foraminifera. A number of features in the shallower of the two cores, including an interval of laminated sediments, are consistent with changes in ventilation over the past 20 kyr suggested by alternations between laminated and bioturbated sediments in the Santa Barbara Basin and the Gulf of California [Keigwin and Jones, 1990; Kennett and Ingram, 1995; Behl and Kennett, 1996]. Data from the deeper of the two California margin cores suggest that during times of reduced ventilation at 800 m, ventilation was enhanced at 1600 m depth, and vice versa. This pronounced depth dependence of ventilation needs to be taken into account when exploring potential teleconnections between the North Pacific and the North Atlantic.

Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.

Temporal variations in arsenic uptake by rice plants in Bangladesh: the role of iron plaque in paddy fields irrigated with groundwater

The transfer of arsenic to rice grains is a human health issue of growing relevance in regions of southern Asia where shallow groundwater used for irrigation of paddy fields is elevated in As. In the present study, As and Fe concentrations in soil water and in the roots of rice plants, primarily the Fe plaque surrounding the roots, were monitored during the 4-month growing season at two sites irrigated with groundwater containing approximately 130microgl(-1) As and two control sites irrigated with water containing <15microgl(-1) As. At both sites irrigated with contaminated water, As concentrations in soil water increased from <10microgl(-1) to >1000microgl(-1) during the first five weeks of the growth season and then gradually declined to <10microgl(-1) during the last five weeks. At the two control sites, concentrations of As in soil water never exceeded 40microgl(-1). At both contaminated sites, the As content of roots and Fe plaque rose to 1000-1500mgkg(-1) towards the middle of the growth season. It then declined to approximately 300mgkg(-1) towards the end, a level still well above As concentration of approximately 100mgkg(-1) in roots and plaque measured throughout the growing season at the two control sites. These time series, combined with simple mass balance considerations, demonstrate that the formation of Fe plaque on the roots of rice plants by micro-aeration significantly limits the uptake of As by rice plants grown in paddy fields. Large variations in the As and Fe content of plant stems at two of the sites irrigated with contaminated water and one of the control sites were also recorded. The origin of these variations, particularly during the last month of the growth season, needs to be better understood because they are likely to influence the uptake of As in rice grains.

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh.

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.

Constraints on the sedimentation history of San Francisco Bay from 14C and 10Be

Abstract Industrialization and urbanization around San Francisco Bay as well as mining and agriculture in the watersheds of the Sacramento and San Joaquin rivers have profoundly modified sedimentation patterns throughout the estuary. We provide some constraints on the onset of these erosional disturbances with 10 Be data for three sediment cores: two from Richardson Bay, a small embayment near the mouth of San Francisco Bay, and one from San Pablo Bay, mid-way between the river delta and the mouth. Comparison of pre-disturbance sediment accumulation determined from three 14 C -dated mollusk shells in one Richardson Bay core with more recent conditions determined from the distribution of 210 Pb and 234 Th [Fuller, C.C., van Geen, A., Baskaran, M., Anima, R.J., 1999. Sediment chronology in San Francisco Bay, California, defined by 210 Pb , 234 Th , 137 Cs , and 239,240 Pu .] shows that the accumulation rate increased by an order of magnitude at this particular site. All three cores from San Francisco Bay show subsurface maxima in 10 Be concentrations ranging in magnitude from 170 to 520×10 6 atoms/g. The transient nature of the increased 10 Be input suggests that deforestation and agricultural development caused basin-wide erosion of surface soils enriched in 10 Be , probably before the turn of the century.

Effect of deep tube well use on childhood diarrhoea in Bangladesh

OBJECTIVE To determine whether the installation of deep tube wells to reduce exposure to groundwater arsenic in rural Bangladesh had an effect on the incidence of childhood diarrhoeal disease. METHODS Episodes of diarrhoeal disease in children aged under 5 years that occurred on one specified day each month between 2005 and 2006 were reported to community health workers for six rural villages. A geographical information system containing details of household water use and sanitation in the villages was built using data obtained by a global positioning system survey. The information system also included health, spatial and demographic data. A field survey was carried out to determine whether households obtained drinking water from deep tube wells installed in 2005. The effect of deep tube well use on the incidence of childhood diarrhoea was assessed using a random effects negative binomial regression model. FINDINGS The risk of childhood diarrhoea was 46% lower in the 179 households that used a deep tube well than in the 364 that used a shallow tube well (P=0.032). Neither socioeconomic status, latrine density, population density nor study year had a significant influence on disease risk. The incidence of childhood diarrhoea declined dramatically between 2005 and 2006, irrespective of water source. CONCLUSION The introduction of deep tube wells to reduce arsenic in drinking water in rural Bangladesh had the additional benefit of lowering the incidence of diarrhoea among young children.

Sensitivity of the North Pacific oxygen minimum zone to changes in ocean circulation: A simple model calibrated by chlorofluorocarbons

[1] Chlorofluorocarbon (CFC) data collected in 1999 at 11 stations along the western margin of Baja California indicate that the oxygen-minimum zone (OMZ) of the area is ventilated from the far North Pacific on decadal timescales. The new data are combined with existing CFC data to constrain a one-dimensional advection-diffusion model that simulates changes in water column properties on the sQ = 26.80 density surface along the path of ventilation. The results show that the penetration of CFCs into the OMZ off Baja California can be explained by slow advection and rapid isopycnal mixing from the southern margin of the Alaskan Gyre. The deficit in dissolved oxygen along the same path relative to conservative behavior is modeled with a consumption term that is the product of a single rate constant and the dissolved oxygen concentration. The model is used to show that very different oceanographic conditions must have prevailed in the North Pacific between 15 and 13 kyr ago, when water containing less than 5 mmol kg � 1 oxygen impinged on a portion of the western margin of North America that was considerably expanded compared to today. To match the distribution of oxygen from the presence of laminations in a series of sediment cores, the least extreme scenario combines a 2.5-fold decrease in advection and diffusion along the current flow path, a 2.5-fold reduction in the oxygen content of ventilated waters of the central North Pacific, and a 2.5-fold increase in the rate constant for oxygen consumption rate, presumably linked to a proportional increase in surface productivity.