Seasonal and short-term controls of riparian oxygen dynamics and the implications for redox processes

Riparian zones are highly-dynamic transition zones between surface water (SW) and groundwater (GW) and function as key biogeochemical-reactors for solutes transitioning between both compartments. Infiltration of SW rich in dissolved oxygen (DO) into the riparian aquifer can supress removal processes of redox sensitive compounds like NO₃⁻, a nutrient harmful for the aquatic ecosystem at high concentrations. Seasonal and short-term variations of temperature and hydrologic conditions can influence biogeochemical reaction rates and thus the prevailing redox conditions in the riparian zone. We combined GW tracer-tests and a 1-year high-frequency dataset of DO with data-driven simulations of DO consumption to assess the effects of seasonal and event-scale variations in temperature and transit-times on the reactive transport of DO. Damköhler numbers for DO consumption (DA_DO) were used to characterize the system in terms of DO turnover potential. Our results suggest that seasonal and short-term variations in temperature are major controls for DO turnover and the resulting concentrations at our field site, while transit-times are of minor importance. Seasonal variations of temperature in GW lead to shifts from transport-limited (DA_DO > 1) to reaction-limited conditions (DA_DO < 1), while short-term events were found to have minor impacts on the state of the system, only resulting in slightly less transport-limited conditions due to decreasing temperature and transit-times. The data-driven analyses show that assuming constant water temperature along a flowpath can lead to an over- or underestimation of reaction rates by a factor of 2–3 due to different infiltrating water temperature at the SW–GW interface, whereas the assumption of constant transit-times results in incorrect estimates of NO₃⁻ removal potential based on DA_DO approach (40%–50% difference).     

Weathering and erosion of fractured bedrock systems

We explore the contribution of fractures (joints) in controlling the rate of weathering advance for a low‐porosity rock by using methods of homogenization to create averaged weathering equations. The rate of advance of the weathering front can be expressed as the same rate observed in non‐fractured media (or in an individual block) divided by the volume fraction of non‐fractured blocks in the fractured parent material. In the model, the parent has fractures that are filled with a more porous material that contains only inert or completely weathered material. The low‐porosity rock weathers by reaction‐transport processes. As observed in field systems, the model shows that the weathering advance rate is greater for the fractured as compared to the analogous non‐fractured system because the volume fraction of blocks is < 1. The increase in advance rate is attributed both to the increase in weathered material that accompanies higher fracture density, and to the increase in exposure of surface of low‐porosity rock to reaction‐transport. For constant fracture aperture, the weathering advance rate increases when the fracture spacing decreases. Equations describing weathering advance rate are summarized in the ‘List of selected equations’. If erosion is imposed at a constant rate, the weathering systems with fracture‐bounded bedrock blocks attain a steady state. In the erosional transport‐limited regime, bedrock blocks no longer emerge at the air‐regolith boundary because they weather away. In the weathering‐limited (or kinetic) regime, blocks of various size become exhumed at the surface and the average size of these exposed blocks increases with the erosion rate. For convex hillslopes, the block size exposed at the surface increases downslope. This model can explain observations of exhumed rocks weathering in the Luquillo mountains of Puerto Rico. Published 2017. This article is a U.S. Government work and is in the public domain in the USA     

Exploring an ‘ideal hill': how lithology and transport mechanisms affect the possibility of a steady state during weathering and erosion

We present a model of chemical reaction within hills to explore how evolving porosity (and by inference, permeability) affects flow pathways and weathering. The model consists of hydrologic and reactive-transport equations that describe alteration of ferrous minerals and feldspar. These reactions were chosen because previous work emphasized that oxygen- and acid-driven weathering affects porosity differently in felsic and mafic rocks. A parameter controlling the order of the fronts is presented. In the absence of erosion, the two reaction fronts move at different velocities and the relative depths depend on geochemical conditions and starting composition. In turn, the fronts and associated changes in porosity drastically affect both the vertical and lateral velocities of water flow. For these cases, estimates of weathering advance rates based on simple models that posit unidirectional constant-velocity advection do not apply. In the model hills, weathering advance rates diminish with time as the Darcy velocities decrease with depth. The system can thus attain a dynamical steady state at any erosion rate where the regolith thickness is constant in time and velocities of both fronts become equal to one another and to the erosion rate. The slower the advection velocities in a system, the faster it attains a steady state. For example, a massive rock with relatively fast-dissolving minerals such as diabase – where solute transport across the reaction front mainly occurs by diffusion – can reach a steady state more quickly than granitoid rocks in which advection contributes to solute transport. The attainment of a steady state is controlled by coupling between weathering and hydrologic processes that force water to flow horizontally above reaction fronts where permeability changes rapidly with depth and acts as a partial barrier to fluid flow. Published 2020. This article is a U.S. Government work and is in the public domain in the USA.     

Evaluation of Amendments to Control Phosphorus Losses in Runoff from Pig Slurry Applications to Land

If spread in excess of crop requirements, incidental phosphorus (P) losses from agriculture can lead to eutrophication of receiving waters. The use of amendments in targeted areas may help reduce the possibility of surface runoff of nutrients. The aim of this study was to identify amendments which may be effective in reducing incidental dissolved reactive phosphorus (DRP) losses in surface runoff from land applied pig slurry. For this purpose, the DRP losses under simulated conditions across the surface of intact grassland soil cores, loaded with unamended and amended slurry at a rate equivalent to 19 kg P ha^?1, were determined over a 30 h period. The effectiveness of the amendments at reducing DRP in overlying water were (in decreasing order): alum (86%), flue gas desulfurization by‐product (FGD) (74%), poly‐aluminum (Al) chloride (PAC) (73%), ferric chloride (71%), fly ash (58%), and lime (54%). FGD was the most costly of all the treatments (€7.64/m³ for 74% removal). Ranked in terms of feasibility, which takes into account effectiveness, cost, and other potential impediments to use, they were: alum, ferric chloride, PAC, fly ash, lime, and FGD.     

Secular variations in seawater chemistry controlling dolomitization in shallow reflux systems: insights from reactive transport modelling

Dolomitization often plays a critical role in the pore network development of platform carbonates, with implications for reservoir quality distribution. Understanding both the hydrological system driving dolomitization and the chemistry of the fluids involved is fundamental to constrain predictions of the geometry and the petrophysical properties of dolomite bodies. Here, the role of secular variations in seawater Mg/Ca as a control on dolomitization and early porosity modification was evaluated using one‐dimensional reactive transport models and fluids based on modern (aragonite sea), Mississippian and Aptian (calcite sea) seawaters. The sensitivity of dolomitization to a range of extrinsic controls (brine salinity, temperature, fluid flow rate and pCO₂) and to intrinsic reactivity of the sediments (effective reactive surface area) was also explored. Simulations suggest faster calcite replacement by dolomite for seawaters with higher Mg/Ca, indicating that dolomitization potential is determined more by Mg/Ca rather than saturation index. Increasing evaporative concentration enhances reaction rate independent of the effect of enhanced density‐driven fluid flux. In addition to brine composition, effective surface area of precursor sediments and temperature exert a critical control on replacement rate, while secular variations of pH and carbonate alkalinity associated with changes in pCO₂ are only secondary controls. Above flow rates of 0·01 m yr^?1 replacive dolomitization is reaction‐limited rather than flux limited, favouring alteration of fine‐grained carbonates and suggesting that preferential alteration of grainstone units is rare unless head gradients are low. Post‐replacement dolomite cementation is flux dependent, and thus favoured in areas of high head gradient and high permeability sediments and, contrary to replacement, supersaturation is a more important driver than Mg/Ca. While uncertainties remain regarding low‐temperature dolomitization kinetics, the capability of numerical simulations to decouple individual controls provides new insights which can be used, in conjunction with traditional comparative sedimentology, to generate more rigorous conceptual models for individual reservoir settings.     

地下水有机污染处理的渗透性反应墙技术

系统介绍了一种新的地下水污染原位治理方法(渗透性反应墙),具体包括渗透性反应墙的布置形式、介质选取、反应机理、应用现状以及存在问题等.在工程实践中,根据现场的水文地质条件和地下水中有机污染物的特点,可以通过改变反应墙的布置形式来有效地截获羽状体.与传统的抽出-处理系统相比,渗透性反应墙具有处理费用低、使用寿命长等特点,特别对高密度非水溶相液体(DNAPLs)形成的污染羽状体有较好的处理效果.     

去耦合方法求解非均质地区地下水中多组分反应-运移模型

近些年来地下水中多组分反应-运移模型在地球科学及环境领域开始得到应用,但其求解较为复杂,为了提高计算效率,可以采用去耦合化方法处理,从而使模型求解得到简化。针对自然界中广泛存在的非均质地质体,提出该类条件下的去耦合化方法,即根据水-岩间、水溶组分间反应的不同,将整个研究区划分为若干子区域,获得对应的去耦合化矩阵。对化学场中各子区域间相邻边界进行设定,达到简化模型求解的目的。最后,以一维非均质介质中基于热力学平衡的反应-运移问题作为算例,基于以上方法进行求解,并与该算例经PHAST软件所示的结果较为一致。结果表明,基于去耦合化方法获得的各离子浓度随时间演变和沿空间分布特征与PHAST所示的结果较为一致,显示该方法在非均质区域模拟溶质运移等方面具有较好的适用性。     

条斑紫菜脱落酸合成对高盐胁迫的响应及其对光合作用的保护

植物在逆境下产生活性氧,诱导抗氧化酶活性、抗逆基因表达上调。采用梯度盐度胁迫的方法处理条斑紫菜,发现高盐胁迫下细胞内脱落酸(ABA)含量随盐度的增加而增加,提示条斑紫菜中可能存在ABA介导的抗氧化代谢通路。利用ABA间接合成途径相关的几种抑制剂处理条斑紫菜叶状体,高盐胁迫诱导氧自由基产生,在藻体复苏过程中通过测定光合作用参数的恢复情况,探测藻体受到的氧化伤害,从而证明条斑紫菜中ABA生物合成的可能路径。结果显示多效唑显著降低了光系统II的电子传递能力,说明条斑紫菜中C5前体的合成是通过类似真菌的MVA途径;萘普生减缓了光合参数的恢复,说明条斑紫菜中ABA合成途径类似于类胡萝卜素参与的间接途径;然而,间接途径合成最后一步的抑制剂钨酸钠却没有影响条斑紫菜胁迫后光合作用参数的恢复,说明条斑紫菜中可能存在经由脱落醇生成ABA的支路途径,而脱落醇可作为活性分子,调控抗氧化酶的表达。烯唑醇则可能引起ABA的分解代谢受到抑制,导致过氧化氢的过度产生,并最终对机体产生不利影响。本文的结果为后续条斑紫菜ABA介导的抗氧化机制解析提供了数据支持。     

Plagioclase weathering in the groundwater system of a sandy,silicate aquifer

The weathering rate of plagioclase was estimated in the groundwater system of a sandy, silicate aquifer formed after the Wisconsin Glacial Stage. The study area is an isthmus lying between Crystal and Big Muskellunge Lakes in northern Wisconsin, USA. Plagioclase occupies 3% of the quartz and K‐feldspar dominated sediments. Groundwater in the study area is recharged in part by precipitation through the isthmus soils and in part by seepage from Crystal Lake, which is of low ionic strength and chemically in steady state. Water analysis revealed that the chemistry of groundwater recharged from Crystal Lake is regulated by mineral dissolution reactions. The rate constant for plagioclase was estimated using mass balances for sodium concentrations along a groundwater flowline from Crystal Lake. For this calculation, various kinds of hydrological/mineralogical information were used: groundwater flow path from oxygen isotope analysis, groundwater travel times from flow modelling, mineral composition from microprobe analysis and surface area of minerals from BET (Brunauer–Emmett–Teller) analysis. The overall range of the estimation was less than an order of magnitude (3·5 × 10^?16 to 3·4 × 10^?15 mol/m²/s). The result is up to three orders of magnitude slower than the previous field estimates, which applied geometric methods in measuring mineral surface areas. However, this result is somewhat higher than the estimates reported by other BET area‐based studies, which were undertaken on soil profiles having different hydrological conditions. This rate difference is interpreted as a result of higher mineral reactivity owing to younger sediment age. The rate difference is smaller when this result is compared with the estimates from the soils of similar age, indicating that the differences in hydrological condition are not sufficient to explain the weathering rate discrepancy between the laboratory and field studies, which is up to five orders of magnitude. Copyright © 2002 John Wiley & Sons, Ltd.     

A coupled transport and reaction model for long column experiments simulating bank filtration

Within the scope of the interdisciplinary Natural and Artificial Systems for Recharge and Infiltration research project dealing with riverbank filtration processes at the Berlin water works, a semi‐technical column experiment has been ongoing since January 2003. Here, a 30 m long soil column is infiltrated with surface water sampled from Lake Tegel (Berlin, Germany) under saturated flow conditions. Changes in pore water hydrochemistry sampled on 21 non‐equidistant distributed points are verified by coupled transport and reaction modelling. The objective of reactive transport modelling was to identify the main biogeochemical processes within the soil column during the flushing experiment as a conceptual model for riverbank filtration. Modelling was done with a combination of MATLAB and PHREEQC. The main processes identified are: (1) biogeochemical degradation due to interaction of natural surface water with the soil matrix; (2) continuous dissolution of refractory air bubbles from the soil column matrix. Copyright © 2006 John Wiley & Sons, Ltd.