Insights into agricultural influences and weathering processes from major ion patterns

Karst areas and their catchments pose a great challenge for protection because fast conduit flow results in low natural attenuation of anthropogenic contaminants. Studies of the hydrochemistry of karst sources and river solutes are an important tool for securing and managing water resources. A study of the geochemical downriver evolution of the Wiesent River and its tributaries, located in a typical karst terrain, revealed unexpected downstream decreases of nitrate with maximum mean values of 30 mg/L at the source to minimum values of 18 mg/L near the river mouth. This trend persisted over the length of the river even though increased agricultural activities are evident in the downstream section of the catchment. This pattern is caused by fertilizer inputs via diffusive and fast conduits flow from karst lithology in the upstream area that may have reached the river's source even from beyond the hydrological catchment boundaries. Further downstream, these influences became diluted by tributary inputs that drain subcatchments dominated by claystone and sandstone lithologies that increased potassium and sulphate concentrations. Our findings indicate that bedrock geology remains the dominant control on the major ion chemistry of the Wiesent River and that agricultural influences are strongest near the headwaters despite increased land use further downstream, due to long‐term storage and accumulation in karst aquifers. This feature may not be unique to the Wiesent River system, as carbonates cover significant portions of the Earth's surface and subsequent work in other river systems could establish whether such patterns are ubiquitous worldwide.     

Efficient DEM‐based overland flow routing using integrated recursive algorithms

Two primary concerns in performing watershed overland flow routing are the numerical instability and computational efficiency. The stability of executing an explicit scheme has to be maintained by observing the Courant–Friedrich–Lewy criterion, which is adopted to confirm that the numerical marching speed is larger than the wave celerity. Moreover, there is another criterion of time step devised in previous studies to avoid back‐and‐forth refluxing between adjacent grids. The situation of refluxing usually occurs on flat regions. In light of this, the selection of a small time increment to honor both restrictions simultaneously is believed to decrease the computational efficiency in performing overland flow routing. This study aims at creating a robust algorithm to relax both restrictions. The proposed algorithm was first implemented on a one‐dimensional overland plane to evaluate the accuracy of the numerical result by comparing it with an analytical solution. Then, the algorithm was further applied to a watershed for 2D runoff simulations. The results show that the proposed integrated algorithm can provide an accurate runoff simulation and achieve satisfactory performance in terms of computational speed.     

The role of eddies in solute transport and recovery in rock fractures: Implication for groundwater remediation

A better understanding of solute transport and retention mechanism in rock fractures has been challenging due to difficulty in their direct observations in microscale rough‐walled fractures. Six representative troughs in a rough‐walled fracture were selected for microscale observations of eddy formation with increasing flow velocity and its effect on spatiotemporal changes of solute concentration. This experimental study was enabled by a microscale visualization technique of micro particle image velocimetry. With increasing flow velocity (Re ≤ 2.86), no eddies were generated, and solutes along the main streamlines transported rapidly, whereas those near the wall moved slowly. A larger amount of solutes remained trapped at all troughs at Re = 2.86 than Re < 1. For Re = 8.57, weak eddies started to be developed at the troughs on the lee side, which little contributed to overall solute flushing in the fracture. Accordingly, a large of amount of water was needed for solute flushing. The flow condition of 1 < Re < 10, before a full development of eddies, was least favourable in terms of time and amount of remediation fluid required to reach a target concentration. After large eddies were fully developed at troughs on the lee side for Re = 17.13, solutes were substantially reduced by eddies with less amount of water. Fully developed eddies were found to enhance solute transport and recovery, as opposed to a general consensus that eddies trap and delay solutes. Direct inflow into troughs on the stoss side also made a great contribution to solute flushing out of the troughs. This study indicates that fully developed eddies or strong inflows at troughs are highly possible to form for Re > 10 and this flow range could be favourable for efficient remediation.     

Drying effects on sorption capacity of coastal sediment: The importance of architecture and polarity of organic matter

Investigations on how desiccation changes sorption of organic compounds by salt marsh sediments provide insight into the physical and chemical properties of these wide-spread coastal sediments. We measured sorption of compounds with different polarities (lysine, tyrosine, naphthalene and aniline) onto natural sediments and sediments that were dried and rewetted. Sorption of lysine by marsh sediment decreased significantly when the sediment was dried using a freeze-drier, oven, or desiccator, and sorption capacity was not restored when sediments were rewetted. In contrast to lysine, the sorption capacity of more hydrophobic compounds (tyrosine, aniline and naphthalene) increased significantly after salt marsh sediment was dried. These results suggest that drying greatly increased sediment hydrophobicity. Consistently, water drop penetration time, an index of hydrophobicity, was significantly lower for combusted sediments than for those that were simply dried. Sediments treated with EDTA, or boiled in seawater, exhibited a similar or even greater reduction in lysine sorption capacity compared with sediments that were dried. Water retention capacity of salt marsh sediment decreased 50% after sediment was dried. The effects of pH and salinity on lysine sorption in wet and dry sediments suggest that carboxyl groups play a major role in lysine sorption through cation ion exchange, and drying may reduce access to carboxyl groups. We hypothesize that the three-dimensional (3D) structure of organic matter, originating mainly from Spartina alterniflora, is an important factor controlling sorption capacity in salt marsh sediment. The drying process makes sedimentary organic matter change conformation, shrink in volume, and expose hydrophobic groups, thus becoming more hydrophobic. In environments with wet and dry cycles, the distribution of hydrophobic or hydrophilic compounds between solution and particulate phases could thus be influenced by the 3D structure and polarity of organic matter.     

Sulfate Reduction and Sulfur Cycles at Two Seagrass Beds Inhabited by Cold Affinity <Emphasis Type="Italic">Zostera marina</Emphasis> and Warm Affinity <Emphasis Type="Italic">Halophila nipponica</Emphasis> in Temperate Coastal Waters

To evaluate the impact of invading seagrass on biogeochemical processes associated with sulfur cycles, we investigated the geochemical properties and sulfate reduction rates (SRRs) in sediments inhabited by invasive warm affinity Halophila nipponica and indigenous cold affinity Zostera marina. A more positive relationship between SRR and below-ground biomass (BGB) was observed at the H. nipponica bed (SRR = 0.6809 × BGB ? 4.3162, r ² = 0.9878, p = 0.0006) than at the Z. marina bed (SRR = 0.3470 × BGB ? 4.0341, r ² = 0.7082, p = 0.0357). These results suggested that SR was more stimulated by the dissolved organic carbon (DOC) exuded from the roots of H. nipponica than by the DOC released from the roots of Z. marina. Despite the enhanced SR in spring-summer, the relatively lower proportion (average, 20%) of acid-volatile sulfur (AVS) in total reduced sulfur and the strong correlation between total oxalate-extractable Fe (Fe_(oxal)) and chromium-reducible sulfur (CRS = 0.2321 × total Fe_(oxal) + 1.8180, r ² = 0.3344, p = 0.0076) in the sediments suggested the rapid re-oxidation of sulfide and precipitation of sulfide with Fe. The turnover rate of the AVS at the H. nipponica bed (0.13 day^?1) was 2.5 times lower than that at the Z. marina bed (0.33 day^?1). Together with lower AVS turnover, the stronger correlation of SRR to BGB in the H. nipponica bed suggests that the extension of H. nipponica resulting from the warming of seawater might provoke more sulfide accumulation in coastal sediments.     

Adsorption characteristics of perchloroethylene in natural sandy materials with low organic carbon content

Laboratory batch tests were conducted to investigate the sorption isotherms and sorption kinetics of the chlorinated hydrocarbon perchloroethylene (PCE) in five natural sandy materials with an organic carbon content (f _oc) in the range 0.080–0.540%. The amended non-linear dual-mode model can describe the sorption isotherms in materials with f _oc in the range 0.080–0.090%. For a sample with a much higher f _oc of 0.54%, the absorption isotherm was found to fit a linear model. These results may indicate that organic carbon is not the main factor influencing the sorption isotherm. The sorption kinetics of PCE in samples with f _oc in the range 0.080–0.090% are not first-order and are different from those observed in the samples with higher f _oc. The sorption process in the materials with lower f _oc involves fast sorption, fast desorption and an equilibrium stage. The results may imply that the factors affecting sorption kinetics of PCE in low f _oc media are pore filling and capillary condensation rather than organic carbon content.     

Effect of agricultural land use on the chemistry of groundwater from basaltic aquifers, Jeju Island, South Korea

Geochemical processes were identified as controlling factors of groundwater chemistry, including chemical weathering, salinization from seawater and dry sea-salt deposition, nitrate contamination, and rainfall recharge. These geochemical processes were identified using principal component analysis of major element chemistry of groundwater from basaltic aquifers in Jeju Island, South Korea, a volcanic island with intense agricultural activities. The contribution of the geochemical processes to groundwater chemistry was quantified by a simple mass-balance approach. The geochemical effects due to seawater were considered based on Cl contributions, whereas the effects due to natural chemical weathering were based on alkalinity. Nitrogenous fertilizers, and especially the associated nitrification processes, appear to significantly affect groundwater chemistry. A strong correlation was observed between Na, Mg, Ca, SO₄ and Cl, and nitrate concentrations in groundwater. Correspondingly, the total major cations, Cl, and SO₄ in groundwater were assessed to estimate relative effect of N-fertilizer use on groundwater chemistry. Cl originates more from nitrate sources than from seawater, whereas SO₄ originates mostly from rainwater. N-fertilizer use has shown the greatest effect on groundwater chemistry, particularly when nitrate concentrations exceed 6–7 mg/L NO₃–N. Nitrate contamination significantly affects groundwater quality and 18% of groundwater samples have contamination-dominated chemistry.     

Biomarker responses in caged rockfish (Sebastes schlegeli) from Masan Bay and Haegeumgang, South Korea

The purpose of this study was to compare enzymatic biomarker activities in fish caged at two sites, Masan Bay (contaminated) and Haeguemgang (reference). In the present study, ethoxyresorufin O-deethylase (EROD), brain acetyl cholinesterase (bAChE), muscle acetyl cholinesterase (mAChE) and butyryl cholinesterase (mBChE) in caged rockfish (Sebastes schlegeli) were measured 0, 1, 3, 7, 14, 21 and 30 days after caging. The level of CYP1A mRNA and Protein expression was induced higher in Masan Bay at 1, 3, 7, 14 and 30 days after caging. EROD activity in the caged fish was significantly higher in Masan Bay than in Haeguemgang 3 and 7 days after caging, but not at 14 and 30 days after caging. bAChE activity was significantly inhibited at 7 and 14 days after caging in Masan Bay. However, mBChE activity was not significantly inhibited during the experiment. Taken together, the data suggest that the caged fish were exposed, at least transiently, to CYP1A inducers and ChE inhibitors, which is consistent with our previous observations.     

Spheroidal pyroxenite aggregates in the Bushveld Complex — a special case of silicate liquid immiscibility

Spherical aggregates of orthopyroxene are reported from some parts of the Bushveld Complex in a variety of host rocks.Detailed mapping has shown that these spherical aggregates, comprising pyroxenite spheroids in a quartz-norite matrix, are contact phenomena and not stratigraphic markers. Orthopyroxene, biotite and amphibole are enriched in spheroids relative to matrix; their mineral chemistry showing a fairly constant orthopyroxene and plagioclase composition through the spheroids and into the matrix, indicating in-situ formation.Bulk chemistry shows spheroid to matrix tie-lines orthogonal to those generally accepted for silicate liquid immiscibility, but other chemical information is consistent with the occurrence of immiscibility.The formation of the aggregates may be related to the industrial process of spherical agglomeration, by which spheroids are formed by the introduction of an immiscible “bridging liquid” to the melt — probably derived from the floor rocks in this case. The mechanism accounts for the field relationships, petrography and chemistry of the aggregate-matrix system. The petrology of the process equates with a special case of silicate liquid immiscibility induced by local contamination and ageing of the original magma.A similar “bridging liquid” mechanism could also account for the formation of the so-called “boulder bed” beneath the Merensky Reef.