Description: A 17-year record (1995–2012) of a suite of environmental tracer concentrations in discharge from 34 springs located along the crest of the Blue Ridge Mountains in Shenandoah National Park (SNP), Virginia, USA, reveals patterns and trends that can be related to climatic and environmental conditions. These data include a 12-year time series of monthly sampling at five springs, with measurements of temperature, specific conductance, pH, and discharge recorded at 30-min intervals. The monthly measurements include age tracers (CFC-11, CFC-12, CFC-113, CFC-13, SF 6 , and SF 5 CF 3 ), dissolved gases (N 2 , O 2 , Ar, CO 2 , and CH 4 ), stable isotopes of water, and major and trace inorganic constituents. The chlorofluorocarbon (CFC) and sulfur hexafluoride (SF 6) concentrations (in pptv) in spring discharge closely follow the concurrent monthly measurements of their atmospheric mixing ratios measured at the Air Monitoring Station at Big Meadows, SNP, indicating waters 0–3 years in age. A 2-year (2001–2003) record of unsaturated zone air displayed seasonal deviations from North American Air of ±10 % for CFC-11 and CFC-113, with excess CFC-11 and CFC-113 in peak summer and depletion in peak winter. The pattern in unsaturated zone soil CFCs is a function of gas solubility in soil water and seasonal unsaturated zone temperatures. Using the increase in the SF 6 atmospheric mixing ratio, the apparent (piston flow) SF 6 age of the water varied seasonally between about 0 (modern) in January and up to 3 years in July–August. The SF 6 concentration and concentrations of dissolved solutes (SiO 2 , Ca 2+ , Mg 2+ , Na + , Cl − , and HCO 3 − ) in spring discharge demonstrate a fraction of recent recharge following large precipitation events. The output of solutes in the discharge of springs minus the input from atmospheric deposition per hectare of watershed area (mol ha −1  a −1 ) were approximately twofold greater in watersheds draining the regolith of Catoctin metabasalts than that of granitic gneisses and granitoid crystalline rocks. The stable isotopic composition of water in spring discharge broadly correlates with the Oceanic Niño Index. Below normal precipitation and enriched stable isotopic composition were observed during El Niño years.

Description: An annual budget for dissolved silica (DSi) and biogenic silica (BSi) was constructed for the Scheldt estuary and for the entire riverine and estuarine Scheldt tidal system (Belgium/The Netherlands) using previously published silica concentrations and fluxes for the period 2003–2005. The annual estuarine DSi mass-balance was established, based on seasonal fluxes estimated using measured DSi concentrations and (fully transient) model simulations of conservative transport. The annual BSi mass-balance was deduced from measured BSi contents in the suspended particulate matter and annual mud fluxes taken from the literature. The Scheldt estuary acted as a net sink not only for the BSi carried by the tidal river as well as that produced by diatoms in the estuary, but also for large amounts of BSi imported from the coastal zone. This results in the retention of dissolved and biogenic silica higher than that of DSi alone, which is in contrast with the classical consideration that rivers act as a source of BSi for the coastal zone. DSi and silica (DSi + BSi) retentions amounted to, respectively, 28 and 64 % in the estuary, and 33 and 66 % in the entire tidal system. This study highlights thus the predominant role of the estuary in the entire Scheldt tidal system when dealing with silica dynamics, as well as the importance of including BSi when investigating estuarine silica retention.

Description: There is a broad correlation between the ε Nd values for rivers (including both the water and the particulate material it carries) and the age of the source terrain. This paper presents Nd isotope distribution data for soil, soil water, groundwater, and stream water samples gathered in a small catchment in northern Sweden. The results show that the release of Nd and Sm from boreal forests into streams and, eventually, into the oceans is more complicated than previously realized. The weathering of till causes changes in both the Nd isotopic composition and Sm/Nd ratios. Both the Sm/Nd ratio and ε Nd were higher in strongly weathered soils horizons than in less weathered till, since minerals with high Sm/Nd ratios were, on average, more resistant to weathering than those with low Sm/Nd ratios. In contrast to the situation for the main minerals and the major elements, the weathering of rare earth elements (REE) was not restricted to the E-horizon: the measured REE concentrations continued to increase with depth in the C-horizon. In addition, REE released by weathering in the upper parts of the soil profile were partly secondarily retained at deeper levels. Therefore, the dissolved Nd released by weathering in the upper soil horizons was trapped and did not enter the groundwater directly. Rather, the Nd in the groundwater largely originated from weathering within the groundwater zone. However, this was not the only source of Nd in the stream water. The Nd isotope composition and Sm/Nd ratio were determined by the mixing between of Nd and Sm in the groundwater and REE-carrying organic material washed out of the soil profile. The groundwater close to the stream reaches the upper soil horizons during high discharge events such as snowmelts, and organic matter carrying Nd and Sm is washed out of the soils and thus released into the stream. Therefore, the Nd exported from catchment is derived from both the weathering within the groundwater zone, and the organic matter washed out from the soil. If longer timescales with more advanced weathering stages in the groundwater zone are considered, it cannot be ruled out that there will be a shift towards more radiogenic values in the exported Nd. Recorded shifts in the Nd isotopic composition in the ocean may thus not only reflect changed source regions, but also the weathering history of the same source region.

Description: Sources and distribution of major and trace elements were investigated in the Plitvice Lakes, a pristine cascade hydrological system of sixteen karst lakes situated in a sparsely populated area of the central Croatia. Water and surface sediment samples from 17 locations, including springs, tributaries and lakes, were analyzed for the content of 22 elements by high-resolution inductively coupled mass spectrometry. Principal component analysis of the collected data set showed that different springs and tributaries displayed distinct multielemental compositions, reflecting primarily the differences in their corresponding geological backgrounds. It was shown that the springs situated in the Upper and Middle Jurassic dolomite bedrock represented the main source of several trace elements, including some toxic metals (Cd, Zn, Ni and Tl), to the Plitvice Lakes system. The concentrations of most of the trace elements (Mn, Fe, Al, Cd, Zn, Cu, Ni, Pb, Co, Cr and Tl) showed decreasing spatial trends in the downstream direction, from sources to the lakes. Such a distribution was interpreted to be a consequence of an efficient removal of the dissolved elements in the lentic parts of the system, mainly by co-precipitation with authigenic calcite and Mn oxides. Nevertheless, most of the elements in the lake sediments were highly correlated with Al, which indicated their prevalent association with terrigenic material. It was shown that the multicascade system of the Plitvice Lakes had an enhanced autopurification efficiency regarding the elimination of most of the trace metals from the aqueous phase.

Description: To quantify chemical weathering and biological uptake, mass-balance calculations were performed on two small forested watersheds located in the Blue Ridge Physiographic Province in north-central Maryland, USA. Both watersheds, Bear Branch (BB) and Fishing Creek Tributary (FCT), are underlain by relatively unreactive quartzite bedrock. Such unreactive bedrock and associated low chemical-weathering rates offer the opportunity to quantify biological processes operating within the watershed. Hydrologic and stream-water chemistry data were collected from the two watersheds for the 9-year period from June 1, 1990 to May 31, 1999. Of the two watersheds, FCT exhibited both higher chemical-weathering rates and biomass nutrient uptake rates, suggesting that forest biomass aggradation was limited by the rate of chemical weathering of the bedrock. Although the chemical-weathering rate in the FCT watershed was low relative to the global average, it masked the influence of biomass base-cation uptake on stream-water chemistry. Any differences in bedrock mineralogy between the two watersheds did not exert a significant influence on the overall weathering stoichiometry. The difference in chemical-weathering rates between the two watersheds is best explained by a larger proportion of reactive phyllitic layers within the bedrock of the FCT watershed. Although the stream gradient of BB is about two-times greater than that of FCT, its influence on chemical weathering appears to be negligible. The findings of this study support the biomass nutrient uptake stoichiometry of K 1.0 Mg 1.1 Ca 0.97 previously determined for the study site. Investigations of the chemical weathering of relatively unreactive quartzite bedrock may provide insight into critical zone processes.

Description: Watershed mass-balance methods are valuable tools for demonstrating impacts to water quality from atmospheric deposition and chemical weathering. Owen Bricker, a pioneer of the mass-balance method, began applying mass-balance modeling to small watersheds in the late 1960s and dedicated his career to expanding the literature and knowledge of complex watershed processes. We evaluated long-term trends in surface-water chemistry in the Loch Vale watershed, a 660-ha. alpine/subalpine catchment located in Rocky Mountain National Park, CO, USA. Many changes in surface-water chemistry correlated with multiple drivers, including summer or monthly temperature, snow water equivalent, and the runoff-to-precipitation ratio. Atmospheric deposition was not a significant causal agent for surface-water chemistry trends. We observed statistically significant increases in both concentrations and fluxes of weathering products including cations, SiO 2 , SO 4 2− , and ANC, and in inorganic N, with inorganic N being primarily of atmospheric origin. These changes are evident in the individual months June, July, and August, and also in the combined June, July, and August summer season. Increasingly warm summer temperatures are melting what was once permanent ice and this may release elements entrained in the ice, stimulate chemical weathering with enhanced moisture availability, and stimulate microbial nitrification. Weathering rates may also be enhanced by sustained water availability in high snowpack years. Rapid change in the flux of weathering products and inorganic N is the direct and indirect result of a changing climate from warming temperatures and thawing cryosphere.

Description: A complex cause–effect type earth systems diagram is presented that represents the interrelation of the global carbon and phosphorus cycles over geological time. It demonstrates how a lot of information can be represented in an extremely compact manner and how relatively unrecognized positive and negative feedbacks are revealed by tracing paths on the diagram. Emphasis is on how the C and P cycles affect the levels of atmospheric CO 2 and O 2 , often via rather indirect paths.

Description: Langat River drains a tropical watershed in the southwest of the Malaysian Peninsula. The watershed is heavily urbanized in its downstream portion. Water samples were collected from May 2010 to December 2011, at three localities along the main stem river, 1 location at its Semenyih tributary and from an upstream groundwater source. Concentration and δ 13 C data of riverine DIC and DOC indicate the dominance of C3 plant-derived material as the primary source of carbon, with δ 13 C DIC values enriched in 13 C relative to that of the C3 source. This enrichment is likely due to CO 2 outgassing, as calculated concentrations of riverine CO 2 are significantly higher than ambient atmospheric values, with methanogenic activity a theoretically possible contributing factor, particularly at the upstream location. The Langat River therefore acts as a net source of CO 2 , with a total sub-basin flux of 19.7 × 10 3  t C year −1 . This is comparable to the sum of riverine DOC, DIC and POC loss rates from the sub-basin, calculated as 24.5 × 10 3  t C year −1 , and highlights the significance of CO 2 evasion from water bodies to the atmosphere for balancing the budget of the terrestrial carbon cycle. The DIC and DOC concentration and δ 13 C data also suggests that in the more urbanized downriver areas, much of the organic carbon input may be anthropogenicaly derived due to ubiquity of sewage treatment plants and landfill sites. Such human-induced perturbations to riverine carbon cycling should be taken into account in future studies of urbanized watersheds.

Description: Biogeochemical processes were investigated in alpine river—Kamniška Bistrica River (North Slovenia), which represents an ideal natural laboratory for studying anthropogenic impacts in catchments with high weathering capacity. The Kamniška Bistrica River water chemistry is dominated by HCO 3 − , Ca 2+ and Mg 2+ , and Ca 2+ /Mg 2+ molar ratios indicate that calcite weathering is the major source of solutes to the river system. The Kamniška Bistrica River and its tributaries are oversaturated with respect to calcite and dolomite. pCO 2 concentrations were on average up to 25 times over atmospheric values. δ 13 C DIC values ranged from −12.7 to −2.7 ‰, controlled by biogeochemical processes in the catchment and within the stream; carbonate dissolution is the most important biogeochemical process affecting carbon isotopes in the upstream portions of the catchment, while carbonate dissolution and organic matter degradation control carbon isotope signatures downstream. Contributions of DIC from various biogeochemical processes were determined using steady state equations for different sampling seasons at the mouth of the Kamniška Bistrica River; results indicate that: (1) 1.9–2.2 % of DIC came from exchange with atmospheric CO 2 , (2) 0–27.5 % of DIC came from degradation of organic matter, (3) 25.4–41.5 % of DIC came from dissolution of carbonates and (4) 33–85 % of DIC came from tributaries. δ 15 N values of nitrate ranged from −5.2 ‰ at the headwater spring to 9.8 ‰ in the lower reaches. Higher δ 15 N values in the lower reaches of the river suggest anthropogenic pollution from agricultural activity. Based on seasonal and longitudinal changes of chemical and isotopic indicators of carbon and nitrogen in Kamniška Bistrica River, it can be concluded that seasonal changes are observed (higher concentrations are detected at low discharge conditions) and it turns from pristine alpine river to anthropogenic influenced river in central flow.

Description: Chemical and water isotope ratios data for groundwaters from the Pozzo del Sale area in the Irpinia sector of the Southern Apennines are presented. The water chemistry of the aquifer system may initially be regarded as the result of easy and common, low temperature interaction between meteoric water and Late Messinian evaporites, which produce Ca-bicarbonate and Na-chloride passing through Ca-sulfate waters. However, a closer inspection reveals a more complicated geochemical setting consisting of: (1) two further Na-sulfate and Ca(Mg)-sulfate waters; (2) the existence of different meteoric recharge areas; (3) the mixing between the different groundwaters and allochthonous fluids from terrestrial mud volcanoes. The salinization mechanism and the local mineralogy were inferred by classical and novel ternary and binary diagrams. The presence of MgSO 4 - and Na 2 SO 4 -bearing minerals of non-marine or mixed origin other than gypsum and halite within the local evaporites suggests a mineralogical heterogeneity within the local Messinian evaporites. The paleoenvironment of this sector of the Gessoso–Solfifera Formation might have been composed of relatively small playa-lakes fed by seawater but also large amounts of continental waters of meteoric origin.