Response to Comment on "Legacy nitrogen may prevent achievement of water quality goals in the Gulf of Mexico".

Ballard et al argue that our prediction of a 30-year or longer recovery time for Gulf of Mexico water quality is highly uncertain, and that much shorter time lags are equally likely. We demonstrate that their argument, based on the use of a two-component regression model, does not sufficiently consider fundamental watershed processes or multiple lines of evidence suggesting the existence of decadal-scale lags.

Transport of chloride and deuterated water in peat: The role of anion exclusion, diffusion, and anion adsorption in a dual porosity organic media.

The dual-porosity structure of peat and the extremely high organic matter content give rise to a complex medium that typically generates prolonged tailing and early 50% concentration breakthrough in the breakthrough curves (BTCs) of chloride (Cl-) and other anions. Untangling whether these observations are due to rate-limited (physical) diffusion into inactive pores, (chemical) adsorption or anion exclusion remains a critical question in peat hydrogeochemistry. This study aimed to elucidate whether Cl- is truly conservative in peat, as usually assumed, and whether the prolonged tailing and early 50% concentration breakthrough of Cl- observed is due to diffusion, adsorption, anion exclusion or a combination of all three. The mobile-immobile (MiM) dual-porosity model was fit to BTCs of Cl- and deuterated water measured on undisturbed cores of the same peat soils, and equilibrium Cl- adsorption batch experiments were conducted. Adsorption of Cl- to undecomposed and decomposed peat samples in batch experiments followed Freundlich isotherms but did not exhibit any trends with the degree of peat decomposition and sorption became negligible below aqueous Cl- concentrations of ~310 mg L-1. The dispersivity determined by fitting the Cl- BTCs whether assuming adsorption or no adsorption were significantly different than determined by the deuterated water (p < .0001). However, no statistical differences in dispersivity (p = .27) or immobile water content (p = .97) was observed between deuterated water and Cl- when accounting for anion exclusion. A higher degree of decomposition significantly increased anion exclusion (p < .0001) but did not influence the diffusion of either tracer into the immobile porosity. Contrary to previous assumptions, Cl- is not truly conservative in peat due to anion exclusion, and adsorption at higher aqueous concentrations, but the overall effect of anion exclusion on transport is likely minimal.

Environmental Indicator Principium with Case References to Agricultural Soil, Water, and Air Quality and Model-Derived Indicators.

Environmental indicators are powerful tools for tracking environmental changes, measuring environmental performance, and informing policymakers. Many diverse environmental indicators, including agricultural environmental indicators, are currently in use or being developed. This special collection of technical papers expands on the peer-reviewed literature on environmental indicators and their application to important current issues in the following areas: (i) model-derived indicators to indicate phosphorus losses from arable land to surface runoff and subsurface drainage, (ii) glutathione-ascorbate cycle-related antioxidants as early-warning bioindicators of polybrominated diphenyl ether toxicity in mangroves, and (iii) assessing the effectiveness of using organic matrix biobeds to limit herbicide dissipation from agricultural fields, thereby controlling on-farm point-source pollution. This introductory review also provides an overview of environmental indicators, mainly for agriculture, with examples related to the quality of the agricultural soil-water-air continuum and the application of model-derived indicators. Current knowledge gaps and future lines of investigation are also discussed. It appears that environmental indicators, particularly those for agriculture, work efficiently at the field, catchment, and local scales and serve as valuable metrics of system functioning and response; however, these indicators need to be refined or further developed to comprehensively meet community expectations in terms of providing a consistent picture of relevant issues and/or allowing comparisons to be made nationally or internationally.

Legacy nitrogen may prevent achievement of water quality goals in the Gulf of Mexico.

In August 2017, the Gulf of Mexico's hypoxic zone was declared to be the largest ever measured. It has been estimated that a 60% decrease in watershed nitrogen (N) loading may be necessary to adequately reduce eutrophication in the Gulf. However, to date there has been no rigorous assessment of the effect of N legacies on achieving water quality goals. In this study, we show that even if agricultural N use became 100% efficient, it would take decades to meet target N loads due to legacy N within the Mississippi River basin. Our results suggest that both long-term commitment and large-scale changes in agricultural management practices will be necessary to decrease Mississippi N loads and to meet current goals for reducing the size of the Gulf hypoxic zone.

Environmental Electrokinetics for a sustainable subsurface.

Soil and groundwater are key components in the sustainable management of the subsurface environment. Source contamination is one of its main threats and is commonly addressed using established remediation techniques such as in-situ chemical oxidation (ISCO), in-situ chemical reduction (ISCR; most notably using zero-valent iron [ZVI]), enhanced in-situ bioremediation (EISB), phytoremediation, soil-washing, pump-and-treat, soil vapour extraction (SVE), thermal treatment, and excavation and disposal. Decades of field applications have shown that these techniques can successfully treat or control contaminants in higher permeability subsurface materials such as sands, but achieve only limited success at sites where low permeability soils, such as silts and clays, prevail. Electrokinetics (EK), a soil remediation technique mostly recognized in in-situ treatment of low permeability soils, has, for the last decade, been combined with more conventional techniques and can significantly enhance the performance of several of these remediation technologies, including ISCO, ISCR, EISB and phytoremediation. Herein, we discuss the use of emerging EK techniques in tandem with conventional remediation techniques, to achieve improved remediation performance. Furthermore, we highlight new EK applications that may come to play a role in the sustainable treatment of the contaminated subsurface.

Microbial selenium sulfide reduction for selenium recovery from wastewater.

Microbial reduction of selenium sulfide (SeS2) is a key step in a new treatment process to recover selenium from selenate and selenite streams. In this process, selenate is first reduced to selenite, and subsequently selenite is reduced by sulfide and precipitates from the solution as SeS2. The latter is bio-reduced to elemental selenium and sulfide. Two anaerobic granular sludges (Eerbeek and Emmtec) were tested for their efficiency to reduce commercial crystalline SeS2. Emmtec sludge had the highest reducing capacity with commercial SeS2 and was therefore also used for the bioreduction of laboratory synthesized amorphous SeS2. Synthesized SeS2 was formed mixing a sulfide solution and effluent containing selenite. With both SeS2 solids (commercial and synthesized SeS2), Emmtec sludge produced sulfide and a solid consisting of hexagonal elemental selenium. The crystalline hexagonal structure suggests the absence of biomolecules, which stabilize amorphous selenium bio-particles under comparable process conditions (T=30°C and a pH between 6 and 7). Selenium particles were not attached to the biomass, suggesting an extracellular formation. The results support the feasibility of the bio-reduction process using sulfur for recovering selenium from water.

Sorption of arsenite, arsenate, and thioarsenates to iron oxides and iron sulfides: a kinetic and spectroscopic investigation.

Sorption to iron (Fe) minerals determines the fate of the toxic metalloid arsenic (As) in many subsurface environments. Recently, thiolated As species have been shown to dominate aqueous As speciation under a range of environmentally relevant conditions, thus highlighting the need for a quantitative understanding of their sorption behavior. We conducted batch experiments to measure the time-dependent sorption of two S-substituted arsenate species, mono- and tetrathioarsenate, and compared it to the sorption of arsenite and arsenate, in suspensions containing 2-line ferrihydrite, goethite, mackinawite, or pyrite. All four As species strongly sorbed to ferrihydrite. For the other sorbents, binding of the thiolated As species was generally lower compared to arsenate and arsenite, with the exception of the near instantaneous and complete sorption of monothioarsenate to pyrite. Analysis of the X-ray absorption spectroscopy (XAS) spectra of sorbed complexes implied that monothioarsenate binds to Fe oxides as a monodentate, inner-sphere complex. In the presence of Fe sulfides, mono- and tetrathioarsenate were both unstable and partially reduced to arsenite. Adsorption of the thiolated As species to the Fe sulfide minerals also caused the substitution of surface sulfur (S) atoms by As and the formation of As-Fe bonds.

Twelve testable hypotheses on the geobiology of weathering.

Critical Zone (CZ) research investigates the chemical, physical, and biological processes that modulate the Earth's surface. Here, we advance 12 hypotheses that must be tested to improve our understanding of the CZ: (1) Solar-to-chemical conversion of energy by plants regulates flows of carbon, water, and nutrients through plant-microbe soil networks, thereby controlling the location and extent of biological weathering. (2) Biological stoichiometry drives changes in mineral stoichiometry and distribution through weathering. (3) On landscapes experiencing little erosion, biology drives weathering during initial succession, whereas weathering drives biology over the long term. (4) In eroding landscapes, weathering-front advance at depth is coupled to surface denudation via biotic processes. (5) Biology shapes the topography of the Critical Zone. (6) The impact of climate forcing on denudation rates in natural systems can be predicted from models incorporating biogeochemical reaction rates and geomorphological transport laws. (7) Rising global temperatures will increase carbon losses from the Critical Zone. (8) Rising atmospheric P(CO2) will increase rates and extents of mineral weathering in soils. (9) Riverine solute fluxes will respond to changes in climate primarily due to changes in water fluxes and secondarily through changes in biologically mediated weathering. (10) Land use change will impact Critical Zone processes and exports more than climate change. (11) In many severely altered settings, restoration of hydrological processes is possible in decades or less, whereas restoration of biodiversity and biogeochemical processes requires longer timescales. (12) Biogeochemical properties impart thresholds or tipping points beyond which rapid and irreversible losses of ecosystem health, function, and services can occur.

Geochemistry of trace metals in a fresh water sediment: field results and diagenetic modeling.

Concentrations of Fe, Mn, Cd, Co, Ni, Pb, and Zn were determined in pore water and sediment of a coastal fresh water lake (Haringvliet Lake, The Netherlands). Elevated sediment trace metal concentrations reflect anthropogenic inputs from the Rhine and Meuse Rivers. Pore water and sediment analyses, together with thermodynamic calculations, indicate a shift in trace metal speciation from oxide-bound to sulfide-bound over the upper 20 cm of the sediment. Concentrations of reducible Fe and Mn decline with increasing depth, but do not reach zero values at 20 cm depth. The reducible phases are relatively more important for the binding of Co, Ni, and Zn than for Pb and Cd. Pore waters exhibit supersaturation with respect to Zn, Pb, Co, and Cd monosulfides, while significant fractions of Ni and Co are bound to pyrite. A multi-component, diagenetic model developed for organic matter degradation was expanded to include Zn and Ni dynamics. Pore water transport of trace metals is primarily diffusive, with a lesser contribution of bioirrigation. Reactions affecting trace metal mobility near the sediment-water interface, especially sulfide oxidation and sorption to newly formed oxides, strongly influence the modeled estimates of the diffusive effluxes to the overlying water. Model results imply less efficient sediment retention of Ni than Zn. Sensitivity analyses show that increased bioturbation and sulfate availability, which are expected upon restoration of estuarine conditions in the lake, should increase the sulfide bound fractions of Zn and Ni in the sediments.

Redox stabilization of the atmosphere and oceans by phosphorus-limited marine productivity

Data from modern and ancient marine sediments demonstrate that burial of the limiting nutrient phosphorus is less efficient when bottom waters are low in oxygen. Mass-balance calculations using a coupled model of the biogeochemical cycles of carbon, phosphorus, oxygen, and iron indicate that the redox dependence of phosphorus burial in the oceans provides a powerful forcing mechanism for balancing production and consumption of atmospheric oxygen over geologic time. The oxygen-phosphorus coupling further guards against runaway ocean anoxia. Phosphorus-mediated redox stabilization of the atmosphere and oceans may have been crucial to the radiation of higher life forms during the Phanerozoic.

Silica precipitation in fractures and the evolution of permeability in hydrothermal upflow zones.

Analytical models are used to compare the rates at which an isolated fracture and vertical, parallel fracture sets in hydrothermal upflow zones can be closed by silica precipitation and thermoelastic stress. Thermoelastic sealing is an order of magnitude faster than sealing by silica precipitation. In vertical fracture sets, both the amount of silica precipitation resulting from cooling and the total thermal expansion of the country rock may be insufficient to seal cracks at depth. These crack systems may ultimately close because the pressure dependence of silica solubility maintains precipitation during upflow even after the temperature gradient vanishes.