Turbidity-Based Sediment Monitoring in Northern Thailand: Hysteresis, Variability, and Uncertainty

Annual total suspended solid (TSS) loads in the Mae Sa River in northern Thailand, determined with an automated, turbidity-based monitoring approach, were approximately 62,000, 33,000, and 14,000 Mg during the three years of observation. These loads were equivalent to basin yields of 839 (603-1170), 445 (217-462), and 192 (108-222) Mg km-2 for the 74.16-km2 catchment during 2006, 2007, and 2008, respectively. The yearly uncertainty ranges indicate our loads may be underestimated by 38-43% or overestimated by 28-33%. In determining the annual loads, discharge (Q) and turbidity (T) values were compared against 333 hand-sampled total suspended solid concentrations (TSS) measured during 18 runoff events and other flow conditions across the three-year period. Annual rainfall varied from 1632 to 1934 mm; and catchment runoff coefficients (annual runoff/annual rainfall) ranged from 0.25 to 0.41. Measured TSS ranged from 8-15,900 mg l-1; the low value was associated with dry-season base flow; the latter, a wet-season storm. Storm size and location played an important role in producing clockwise, anticlockwise, and complex hysteresis effects in the Q-TSS relationship. Turbidity alone was a good estimator for turbidity ranges of roughly 10-2800 NTU (or concentrations approximately 25-4000 mg l-1). However, owing to hysteresis and high sediment concentrations that surpass the detection limits of the turbidity sensor during many annual storms, TSS was estimated best using a complex multiple regression equation based on high/low ranges of turbidity and Q as independent variables. Turbidity was not a good predictor of TSS fractions \u3e 2000 μm. Hysteresis in the monthly Q-TSS relationship was generally clockwise over the course of the monsoon season, but infrequent large dry-season storms disrupted the pattern in some years. The large decrease in annual loads during the study was believed to be related to depletion of fine sediment delivered to the stream by several landslides occurring the year prior to the study. The study indicated the importance of monitoring Q and turbidity at fine resolutions (e.g., sub-hourly) to capture the TSS dynamics and to make accurate load estimations in this flashy headwater stream where hysteresis in the Q-TSS signature varied at several time scales

Deciphering and Predicting Spatial and Temporal Concentrations of Arsenic Within the Mekong Delta Aquifer

Unravelling the complex, coupled processes responsible for the spatial distribution of arsenic within groundwaters of South and South-East Asia remains challenging, limiting the ability to predict the subsurface spatial distribution of arsenic. Previous work illustrates that Himalayan-derived, near-surface (0 to 12 m) sediments contribute a substantial quantity of arsenic to groundwater, and that desorption from the soils and sediments is driven by the reduction of AsV and arsenic-bearing iron (hydr)oxides. However, the complexities of groundwater flow will ultimately dictate the distribution of arsenic within the aquifer, and these patterns will be influenced by inherent physical heterogeneity along with human alterations of the aquifer system. Accordingly, we present a unified biogeochemical and hydrologic description of arsenic release to the subsurface environment of an arsenic-afflicted aquifer in the Mekong Delta, Kandal Province, Cambodia, constructed from measured geochemical profiles and hydrologic parameters. Based on these measurements, we developed a simple yet dynamic reactive transport model to simulate one- and two-dimensional geochemical profiles of the near surface and aquifer environment to examine the effects of subsurface physical variation on the distribution of arsenic. Our results show that near-surface release (0–12 m) contributes enough arsenic to the aquifer to account for observed field values and that the spatial distribution of arsenic within the aquifer is strongly affected by variations in biogeochemical and physical parameters. Furthermore, infiltrating dissolved organic carbon and ample buried particulate organic carbon ensures arsenic release from iron (hydr)oxides will occur for hundreds to thousands of years

A Simplified Approach for Estimating Soil Carbon and Nitrogen Stocks in Semi-Arid Complex Terrain

We investigated soil carbon (C) and nitrogen (N) distribution and developed a model, using readily available geospatial data, to predict that distribution across a mountainous, semi-arid, watershed in southwestern Idaho (USA). Soil core samples were collected and analyzed from 133 locations at 6 depths (n=798), revealing that aspect dramatically influences the distribution of C and N, with north-facing slopes exhibiting up to 5 times more C and N than adjacent southfacing aspects. These differences are superimposed upon an elevation (precipitation) gradient, with soil C and N contents increasing by nearly a factor of 10 from the bottom (1100 m elevation) to the top (1900 m elevation) of the watershed. Among the variables evaluated, vegetation cover, as represented by a Normalized Difference Vegetation Index (NDVI), is the strongest, positively correlated, predictor of C; potential insolation (incoming solar radiation) is a strong, negatively correlated, secondary predictor. Approximately 62% (as R2) of the variance in the C data is explained using NDVI and potential insolation, compared with an R2 of 0.54 for a model using NDVI alone. Soil N is similarly correlated to NDVI and insolation. We hypothesize that the correlations between soil C and N and slope, aspect and elevation reflect, in part, the inhibiting influence of insolation on semi-arid ecosystem productivity via water limitation. Based on these identified relationships, two modeling techniques (multiple linear regression and cokriging) were applied to predict the spatial distribution of soil C and N across the watershed. Both methods produce similar distributions, successfully capturing observed trends with aspect and elevation. This easily applied approach may be applicable to other semi-arid systems at larger scales

Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow

Iron (hydr)oxides not only serve as potent sorbents and repositories for nutrients and contaminants but also provide a terminal electron acceptor for microbial respiration. The microbial reduction of Fe (hydr)oxides and the subsequent secondary solid-phase transformations will, therefore, have a profound influence on the biogeochemical cycling of Fe as well as associated metals. Here we elucidate the pathways and mechanisms of secondary mineralization during dissimilatory iron reduction by a common iron-reducing bacterium, Shewanella putrefaciens (strain CN32), of 2-line ferrihydrite under advective flow conditions. Secondary mineralization of ferrihydrite occurs via a coupled, biotic-abiotic pathway primarily resulting in the production of magnetite and goethite with minor amounts of green rust. Operating mineralization pathways are driven by competing abiotic reactions of bacterially generated ferrous iron with the ferrihydrite surface. Subsequent to the initial sorption of ferrous iron on ferrihydrite, goethite (via dissolution/reprecipitation) and/or magnetite (via solid-state conversion) precipitation ensues resulting in the spatial coupling of both goethite and magnetite with the ferrihydrite surface. The distribution of goethite and magnetite within the column is dictated, in large part, by flow-induced ferrous Fe profiles. While goethite precipitation occurs over a large Fe(II) concentration range, magnetite accumulation is only observed at concentrations exceeding 0.3 mmol/L (equivalent to 0.5 mmol Fe[II]/g ferrihydrite) following 16 d of reaction. Consequently, transportregulated ferrous Fe profiles result in a progression of magnetite levels downgradient within the column. Declining microbial reduction over time results in lower Fe(II) concentrations and a subsequent shift in magnetite precipitation mechanisms from nucleation to crystal growth. While the initial precipitation rate of goethite exceeds that of magnetite, continued growth is inhibited by magnetite formation, potentially a result of lower Fe(III) activity. Conversely, the presence of lower initial Fe(II) concentrations followed by higher concentrations promotes goethite accumulation and inhibits magnetite precipitation even when Fe(II) concentrations later increase, thus revealing the importance of both the rate of Fe(II) generation and flow-induced Fe(II) profiles. As such, the operating secondary mineralization pathways following reductive dissolution of ferrihydrite at a given pH are governed principally by flow-regulated Fe(II) concentration, which drives mineral precipitation kinetics and selection of competing mineral pathways

Spatial and Temporal Dynamics of Dissolved Oxygen Concentrations and Bioactivity in the Hyporheic Zone

Dissolved oxygen (DO) concentrations and consumption rates are primary indicators of heterotrophic respiration and redox conditions in the hyporheic zone (HZ). Due to the complexity of hyporheic flow and interactions between hyporheic hydraulics and the biogeochemical processes, a detailed, mechanistic, and predictive understanding of the biogeochemical activity in the HZ has not yet been developed. Previous studies of microbial activity in the HZ have treated the metabolic DO consumption rate constant (KDO) as a temporally fixed and spatially homogeneous property that is determined primarily by the concentration of bioavailable carbon. These studies have generally treated bioactivity as temporally steady state, failing to capture the temporal dynamics of a changeable system. We demonstrate that hyporheic hydraulics controls rate constants in a hyporheic system that is relatively abundant in bioavailable carbon, such that KDO is a linear function of the local downwelling flux. We further demonstrate that, for triangular dunes, the downwelling velocities are lognormally distributed, as are the KDO values. By comparing measured and modeled DO profiles, we demonstrate that treating KDO as a function of the downwelling flux yields a significant improvement in the accuracy of predicted DO profiles. Additionally, our results demonstrate the temporal effect of carbon consumption on microbial respiration rates

Peat Formation Concentrates Arsenic Within Sediment Deposits of the Mekong Delta

Mekong River Delta sediment bears arsenic that is released to groundwater under anaerobic conditions over the past several thousand years. The oxidation state, speciation, and distribution of arsenic and the associated iron bearing phases are crucial determinants of As reactivity in sediments. Peat from buried mangrove swamps in particular may be an important host, source, or sink of arsenic in the Mekong Delta. The total concentration, speciation, and reactivity of arsenic and iron were examined in sediments in a Mekong Delta wetland by X-ray fluorescence spectrometry (XRF), X-ray absorption spectroscopy (XAS), and selective chemical extractions. Total solid-phase arsenic concentrations in a peat layer at a depth of 6 m below ground increased 10-fold relative to the overlying sediment. Extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that arsenic in the peat was predominantly in the form of arsenian pyrite. Arsenic speciation in the peat was examined further at the micron-scale using μXRF and μX-ray absorption near-edge structure (XANES) spectroscopy coupled with principal component analysis. The multiple energy μXRF mapping and μXANES routine was repeated for both iron and sulfur phase analyses. Our μXRF/μXANES analyses confirm arsenic association with pyrite – a less reactive host phase than iron (hydr)oxides under anaerobic conditions. The arsenian pyrite likely formed upon deposition/formation of the peat in a past estuarine environment (∼ 5.5 ka BP), a process that is not expected under current geochemical conditions. Presently, arsenian pyrite is neither a source nor a sink for aqueous arsenic in our sediment profile, and under present geochemical conditions represents a stable host of As under the reducing aquifer conditions of the Mekong Delta. Furthermore, organic carbon within the peat is unable to fuel Fe(III) reduction, as noted by the persistence of goethite which can be reduced microbially with the addition of glucose