We developed a process-based model to predict the probability of arsenic exceeding 5 microg/L in drinking water wells in New England bedrock aquifers. The model is being used for exposure assessment in an epidemiologic study of bladder cancer. One important study hypothesis that may explain increased bladder cancer risk is elevated concentrations of inorganic arsenic in drinking water. In eastern New England, 20-30% of private wells exceed the arsenic drinking water standard of 10 micrograms per liter. Our predictive model significantly improves the understanding of factors associated with arsenic contamination in New England. Specific rock types, high arsenic concentrations in stream sediments, geochemical factors related to areas of Pleistocene marine inundation and proximity to intrusive granitic plutons, and hydrologic and landscape variables relating to groundwater residence time increase the probability of arsenic occurrence in groundwater. Previous studies suggest that arsenic in bedrock groundwater may be partly from past arsenical pesticide use. Variables representing historic agricultural inputs do not improve the model, indicating that this source does not significantly contribute to current arsenic concentrations. Due to the complexity of the fractured bedrock aquifers in the region, well depth and related variables also are not significant predictors.

Our findings support an association between low-to-moderate levels of arsenic in drinking water and bladder cancer risk in New England. In addition, historical consumption of water from private wells, particularly dug wells in an era when arsenical pesticides were widely used, was associated with increased bladder cancer risk and may have contributed to the New England excess.

Abstract:The adequacy of mineral resources in light of population growth and rising standards of living has been a concern since the time of Malthus (1798), but many studies erroneously forecast impending peak production or exhaustion because they confuse reserves with "all there is". Reserves are formally defined as a subset of resources, and even current and potential resources are only a small subset of "all there is". Peak production or exhaustion cannot be modeled accurately from reserves. Using copper as an example, identified resources are twice as large as the amount projected to be needed through 2050. Estimates of yet-to-be discovered copper resources are up to 40-times more than currently-identified resources, amounts that could last for many centuries. Thus, forecasts of imminent peak production due to resource exhaustion in the next 20-30 years are not valid. Short-term supply problems may arise, however, and supply-chain disruptions are possible at any time due to natural disasters (earthquakes, tsunamis, hurricanes) or political complications. Needed to resolve these problems are education and exploration technology development, access to prospective terrain, better recycling and better accounting of externalities associated with production (pollution, loss of ecosystem services and water and energy use).

Experimental studies, using cold-seal and extraction vessel techniques, were conducted on Fe, Pb, Zn, and Cu sulfide solubilities in chloride solutions at temperatures from 300 ø to 700øC and pressures from 0.5 to 2 kbars. The solutions were buffered in pH by a quartz monzonite and the pure potassium feldspar-muscovite-quartz assemblage and inj•2-fo 2 largely by the assemblage pyrite-pyrrhotite-magnetite.Solubilities increase with increasing temperature and total chloride, and decrease with increasing pressure. The rise in solubility is particularly steep between 300 ø and 500øC and between 1,000 and 500 bars. With increasing temperature at any given pressure, or with decreasing pressure at any given temperature, metal solubility eventually passes through a maximum due to increasing competition for chloride by the alkali, hydrogen, and base metal ions and because intersection with a two-fluid region eventually occurs. In that portion of the two-fluid region encountered in the study, metal solubilities in the brine were very high, but solubilities in the gas phase also were significant. In a system controlled by the potassium feldspar-muscovite-quartz buffer, 1-m total CI-, and the assemblage pyrite-pyrrhotite-magnetite-sphalerite-galena-chalcopyrite, solubilities in ppm at 1 kbar and 300% 400 ø, and 500øC were 237, 1,216, and 5,636, for Fe; 5l, 613, and 3,105 for Pb; 36, 423, and 2,649 for Zn; and 11, 40, and 113 for Cu, respectively. At 400øC, 0.5 and 2 kbars, the values were 2,627 and 500 for Fe; 1,262 and 194 for Pb; 983 and 120 for Zn; and 60 and 29 for Cu, respectively. All of the above were in the single-fluid region. Single-metal solubilities also were investigated to assess the influence of iron on the solubility of the other metals and to corroborate preliminary dissociation constants for the metal chloride complexes involved.The effect of increasing chloride concentration on solubility reflects primarily a shift to lower pH via the silicate buffer reactions. The effect of decreasing pressure reflects primarily the relative change in the dissociation constants of the chloride complexes involved. Increasing sulfur fugacity lowers solubility, but in systems controlled at relatively low values by an rs2 buffer or wall-rock sulfidation reactions, solutions of high metal content relative to reduced sulfur will tend to develop at high chloride concentrations.Similarity in behavior with respect to the temperature and pressure of Fe, Zn, and Pb sulfide solubilities points to similarity in chloride speciation, and the neutral species appear to be dominant in the high-temperature region. At 500øC and l kbar, the log KD values for FeCI•, PbCI•, ZnCI•, and CuC1 ø are, respectively, -8.76, -9.14, -10.86, and -6.22.