UV spectrometry for measuring particulate organic matter in natural water

Ultraviolet (UV) spectra were measured to characterize the dissolved and particulate organic matter in a bog and to investigate the seasonal fluctuation of this organic matter. The optical density spectra in the UV region of dissolved organic matter (DOM) were proportional to ^–4, where is the wavelength of incident light. There was also small absorption on the ^–4 spectra. The optical density at a wavelength of 280 nm was proportional to the concentration of dissolved organic carbon (DOC). The spectra and the dependency of optical density on DOC did not vary throughout the investigation period. The UV spectra of acid extractions of particulate organic matter (POM) showed two absorption peaks at the wavelengths of 220 nm and 335 nm. These peaks are well represented by the sum of two Lorentz functions. The ratio of the absorbances,A ₂₈₀/A ₃₃₅, was dependent on the nitrogen/carbon ratio of POM and the chlorophyll fraction in particulate organic carbon (POC), and not dependent on POC itself. The dependency of POC absorption at 280 nm varied with this ratio which fluctuated seasonally.     

Discrete suspended particles of barite and the barium cycle in the open ocean

Barite particles are a universal component of suspended matter in the Atlantic and Pacific Oceans. This is demonstrated by scanning electron microscope and electron microprobe analyses of samples collected during the GEOSECS program. These discrete particles, about 1 μm in diameter, account for by far the greatest part of the total particulate barium of most of the filters collected at different depths. Total particulate barium (mean value: 20 ng/kg seawater) was measured on the same filters by instrumental neutron activation analysis.Several observations indicate that biochemical, rather than purely chemical, processes are involved in the formation of the BaSO₄ mineral in the water column. Sr/Ba molar ratios among the individual barite grains, particularly from surface waters are extremely variable, which would not be anticipated for purely chemical interactions. Barite crystals occurring within fecal debris have been observed throughout the water column. Within such debris decomposition of the abundant organic matter may provide the micro-environment predicted as necessary for the precipitation of BaSO₄. Finally, a strong correlation between nutrient content and particulate barium is found in the upper 1000 m of the water column, which also suggests a control of barite formation by biota.Some of the barite dissolves at depth in the water column. Dissolution rates were calculable for two GEOSECS stations, from which a dissolved barium flux of 0.4 μg/cm² yr was deduced. This figure is of the same order as the dissolved barium flux calculable from the barium content and known dissolution rates of calcareous and siliceous tests: approximately 0.5 μg/cm² yr. These fluxes represent the largest source of dissolved barium in the water column, the other being river input (0.6 μg/cm² yr). This supports the contention that the barium in the water column is mostly recycled. The residual flux of barite-Ba reaching the sea floor is of about equal importance as the flux of barium associated with fast-settling fecal material. These two sources together are almost sufficient to account for the total sedimentation rate of barium.     

Th:U disequilibrium as an indicator of sediment resuspension in Thermaikos Gulf, northwestern Aegean Sea

²³⁴Th:²³⁸U disequilibria have been used extensively as tracers of particle dynamics in marine environments. ²³⁴Th (t_1/2=24.1 days) can be used as “proxy” for particle reactive pollutants, due to their similar rapid rate of scavenging onto particles and subsequent removal from the water column, to the sediments. Radioactive disequilibrium can be exploited to determine the rates and time-scales of processes occurring over days to months; in this instance the residence times of dissolved and particulate species with the benthic nepheloid layer (BNL).Three sampling cruises were undertaken in Thermaikos Gulf (NW Aegean Sea) during contrasting periods, to examine the impact of natural and anthropogenic activity on sediment resuspension. September and October 2001 represented background and trawling periods, respectively; January 2002 represented a mixed period, of trawling and storms.Dissolved ²³⁴Th is scavenged actively at the BNL, in the presence of suspended particulate material (SPM), with a mean residence time of 16 days. There is a weak inverse correlation between dissolved ²³⁴Th residence time and SPM concentration in the BNL, with the shortest residence times occurring during October 2001. No relationship was observed between particulate ²³⁴Th activities and SPM concentrations, indicating that particles are rapidly removed from the system, either by sinking or advection. The mean particulate ²³⁴Th residence time is 5 days.     

Maintenance of estuarine water quality by mangroves occurs during flood periods: A case study of a subtropical mangrove wetland

Seasonal changes in water quality were measured in samples taken at various distances from shallow water across mudflat to mangroves during flood period and from mangroves across mudflat to shallow water during ebb period in a subtropical mangrove estuary (Zhangjiang Estuary, Fujian, China). The TN (total dissolved nitrogen), TP (total dissolved phosphorus), COD (chemical oxygen demand), and DOC (dissolved organic carbon) contents during the flood period were significantly higher than those during the ebb period. In contrast, the opposite was true for the POC (particulate organic carbon) content and transparency. The mangroves at Zhangjiang Estuary may trap nutrients at rates of 90.5 g N/m²/yr, 2.2 g TP/m²/yr, and 13.7 g C/m²/yr in the form of DOC, and export POC at a rate of 81.8 g/m²/yr. Our results support the hypothesis that the maintenance of estuarine water quality by mangroves occurs during flood periods.     

Comments on some aspects of particulate transport in the oceans

Recent studies of dissolved and particulate concentrations of trace elements and radionuclides amply demonstrate the importance of particulate transport in the case of several elements. A significant in-situ addition (J-flux) or removal (J-efflux) occurs in the case of a number of elements. However, to date it is not clear how the particulate processes occur and how the particles themselves are transported. Some of the problems are outlined briefly.It is shown that whereas a substantial flux in the case of some elements is due to transport by consolidated fecal particles, this transport does not generally lead to any substantial in-situ addition to deep waters. Changes in the dissolved concentrations of elements within the oceans occur due to small particles (1–10 μm) which sink stochastically with a mean speed of ～10^?3 cm/s. The larger particles sinking at higher Stokes' velocities impact and carry along the small particles. The smaller particles, ～1 μm size are thus transported down rapidly by the larger particles by apiggy-back mechanism. Simple theoretical calculations are consistent with the measured vertical transport rates based on studies of radionuclides.     

Distribution of uranium isotopes in the main channel of Yellow river (Huanghe), China

Uranium isotopes were measured in waters and suspended particulate matters (SPM) of the main channel of Yellow River, China that were sampled during four field trips between August 2005 and July 2006. The results show that the concentration of dissolved U (2.04–7.83 μg/l) and the activity ratio of ²³⁴U/²³⁸U (1.36–1.67) are much higher than the average U concentrations and activity ratios of global major rivers. Mass balance calculations using the results of simulated experiments and measurement data show that the section of the Yellow River between Lanzhou and Sanmenxia has its dissolved U derived from two sources: suspended sediments (68%) and groundwater/runoff from loess deposits (32%). Both sources are related to the heavy erosion of the Chinese Loess Plateau.     

226Ra,210Pb and210Po in the Red Sea

Profiles of²²⁶Ra and dissolved²¹⁰Pb have been measured at several stations in the Red Sea. At one station in the central Red Sea an expanded profile was measured including²²⁶Ra and dissolved and particulate²¹⁰Pb and²¹⁰Po. These profiles show several distinct features: (1)²²⁶Ra displays a mid-depth maximum of about 13 dpm/100 kg at about 500 m; (2) dissolved²¹⁰Pb concentrations are uniformly low at about 2 dpm/100 kg with little lateral or vertical variation; (3) the surface-water²¹⁰Pb excess which is commonly observed in low-latitude open ocean regions is entirely lacking; (4)²¹⁰Pb and²¹⁰Po activities are essentially identical to each other in both particulate and dissolved phases although²¹⁰Po activities appear somewhat lower; (5) about 20% of the²¹⁰Pb and²¹⁰Po in the water column residues on particulate matter.Assuming the atmospheric²¹⁰Pb flux to be in the dissolved form and at the lower level of the normal range i.e. 0.5 dpm/cm² yr, the residence time of the dissolved Pb is about 1.5 years. However, if the same atmospheric flux is entirely in particulate form, then the residence time of the dissolved Pb is about 5 years. The residence time of Pb in the particulate phase is less than 0.4 years if all the Pb is removed only by sinking particles.     

VERTEX: manganese transport through oxygen minima

Manganese transport through a well-developed oxygen minimum was studied off central Mexico (18°N, 108°W) in October–November 1981 as part of the VERTEX (Vertical Transport and Exchange) research program. Refractory, leachable and dissolved Mn fractions associated with particulates caught in traps set at eight depths (120–1950 m) were analyzed. Particles entering the oxygen minimum had relatively large Mn loads; however, as the particulates sank further into the minimum, total Mn fluxes steadily decreased from 190 nmol m^?2 day^?1 at 120 m to 36 nmol m^?2 day^?1 at 400 m. Manganese fluxes then steadily increased in the remaining 800–1950 m, reaching rates of up to 230 nmol m^?2 day^?1 at 1950 m.Manganese concentrations were also measured in the water column. Dissolved Mn levels < 3.0 nmol kg^?1 were consistently observed within the 150–600 m depth interval. In contrast, suspended particulate leachable Mn amounts were especially low at those depths, and never exceeded 0.04 nmol kg^?1.The combined water column and particle trap data clearly indicate that Mn is released from particles as they sink through the oxygen minimum. Rate-of-change estimates based on trap flux data yield regeneration rates of up to 0.44 nmol kg^?1 yr^?1 in the upper oxygen minimum (120–200 m). However, only 30% of the dissolved Mn in the oxygen minimum appears to be from sinking particulate regeneration; the other 70% probably results from continental-slope-release-horizontal-transport processes.Dissolved Mn scavenges back onto particles as oxygen levels begin to increase with depth. Scavenging rates ranging from ?0.03 to ?0.09 nmol kg^?1 yr^?1 were observed at depths from 700 to 1950 m. These scavenging rates result in Mn residence times of 16–19 years, and scavenging rate constants on the order of 0.057 yr^?1. Manganese removal via scavenging on sinking particles below the oxygen minimum is balanced by Mn released along continental boundaries and transported horizontally via advective-diffusive processes.Manganese appears to be very weakly associated with particulates. Nevertheless, the amounts of Mn involved with sinking biogenic particles are large, and the resulting fluxes are on the same order of magnitude as those necessary to explain the excess Mn accumulating on the sea floor. The overall behavior of Mn observed in this, and other, studies strongly suggests some type of equilibrium occurring between dissolved and particulate phases. This equilibrium appears to shift in direct or indirect response to dissolved oxygen levels.     

Lithological and hydrological controls on water composition: evaporite dissolution and glacial weathering in the south central Andes of Argentina (33°–34°S)

Lithological and hydrological influence on fluvial physical and chemical erosion was studied in a glacierized sedimentary basin with high evaporite presence. Suspended particulate matter (SPM), total dissolved solids (TDS) and major ion concentrations were analysed for 2 years of different hydrologic condition: (i) 2009–2010, Q = 100% average; and (ii) 2010–2011, Q = 60% average. Annual hydrograph was simple regime‐type with one peak in summer related to snow melting. The intra‐annual SPM and TDS variations were directly and inversely associated to Q, respectively. Snow chemistry showed continental influence (Na⁺/Ca²⁺ = 0.17), and atmospheric input of TDS was <1% of the total exported flux. River water was highly concentrated in Ca²⁺ and SO₄²⁻ (~4 mmol l⁻¹) and in Na⁺ and Cl⁻ (~3 mmol l⁻¹). Ca²⁺/SO₄²⁻ and Na⁺/Cl⁻ molar ratios were ~1 and related to Q, directly and inversely, respectively. Major ion relationships suggest that river chemistry is controlled by evaporite (gypsum and halite) dissolution having a summer input from sulfide oxidation and carbonate dissolution, and a winter input from subsurface flow loaded with silicate weathering products. This variation pattern resulted in nearly chemostatic behaviour for Ca⁺, Mg²⁺ and SO₄²⁻, whereas Na⁺, Cl⁻ and SiO₂ concentrations showed to be controlled by dilution/concentration processes. During the 2009–2010 hydrological year, the fluxes of water, SPM and TDS registered in the snow melting–high Q season were, respectively, 71%, 92% and 67% of the annual total, whereas for equal period in 2010–2011, 56% of water, 86% of SPM and 54% of TDS annual fluxes were registered. The SPM fluxes for 2009–2010 and 2010–2011 were 1.19 × 10⁶ and 0.79 × 10⁶ t year⁻¹, whereas TDS fluxes were 0.68 × 10⁶ and 0.55 × 10⁶ t year⁻¹, respectively. Export rates for 2009–2010 were 484 t km² year⁻¹ for SPM and 275 t km² year⁻¹ for TDS. These rates are higher than those observed in glacierized granite basins and in non‐glacierized evaporite basins, suggesting a synergistic effect of lithology and glaciers on physical and chemical erosion. Copyright © 2014 John Wiley & Sons, Ltd.     

Phosphorus Forms and Their Changes in Water of Three Subalpine Lakes in Italy

Total phosphorus and its main forms: dissolved mineral, dissolved organic, particulate organic and particulate mineral in the vertical water column of three subalpine lakes of various types in Italy, has been estimated during the winter-vernal season. The range of variation in the phosphorus content in these waters was as follows: total phosphorus 16 ± 2860 μg/1 PO₄, dissolved mineral phosphorus 4 ± 1040 μg/l PO₄, dissolved organic phosphorus 1 ± 160μg/l PO₄, particulate organic phosphorus 0 ± 290 μg/l PO₄ and particulate mineral phosphorus 1 ± 100 μg/l PO₄, Generally the content of total phosphorus and dissolved mineral phosphorus (phosphates) increased with the degree of eutrophy with the depth and with the progress of the vernal season towards the summer stagnation time. The amount of phosphates increased in water with the depletion of oxygen, both in the verical water column and with the progress of stagnation time. The amounts of dissolved organic phosphorus decressed with the depth of the vertical water column whereas the dissolved mineral phosphorus increased. The development of the particulate organic phosphorus stratification in the vertical water column was clearly visible in the eutrophic lake. The quantities of total phosphorus and its main component, dissolved mineral phosphorus, decreased evidently from January to May in all three lakes, mostly in the eutrophic lake. The reason of this decrease is sorption by lake sediments and to a certain degree sedimentation of phosphorus sorbed by ferric hydroxide. The increase of dissolved mineral phosphorus and that of total phosphorus in the vertical water column and with the progress of summer stagnation had as a reason the liberation of phosphorus from sediments, and not so much decomposition of sedimentating plankton or dissolved organic phosphorus. The share of single (mean) values of phosphorus forms in the total phosphorus was as follows: In the oligotrophic lake the share of particulate mineral phosphorus was extremely high in March (21% of the total), probably because of the inflow of the melting waters from the drainage area. The development of vertical stratification in waters of three subalpine Italian lakes at the end of the vernal season (May) indicates the quantitative prevailing of dissolved mineral phosphorus with its increase with the depth and domination of dissolved organic phosphorus in the trophogenic zone.     

Chemical and Isotopic Composition of Waters and Dissolved Gases in Some Thermal Springs of Sicily and Adjacent Volcanic Islands, Italy

Hydrochemical (major and some minor constituents), stable isotope ( and , δ13C_TDIC total dissolved inorganic carbon) and dissolved gas composition have been determined on 33 thermal discharges located throughout Sicily (Italy) and its adjacent islands. On the basis of major ion contents, four main water types have been distinguished: (1) a Na-Cl type; (2) a Ca-Mg > Na-SO₄-Cl type; (3) a Ca-Mg-HCO₃ type and (4) a Na-HCO₃ type water. Most waters are meteoric in origin or resulting from mixing between meteoric water and heavy-isotope end members. In some samples, δ¹⁸O values reflect the effects of equilibrium processes between thermal waters and rocks (positive ¹⁸O-shift) or thermal waters and CO₂ (negative ¹⁸O-shift). Dissolved gas composition indicates the occurrence of gas/water interaction processes in thermal aquifers. N₂/O₂ ratios higher than air-saturated water (ASW), suggest the presence of geochemical processes responsible for dissolved oxygen consumption. High CO₂ contents (more than 3000 cc/litre STP) dissolved in the thermal waters indicate the presence of an external source of carbon dioxide-rich gas. TDIC content and δ¹³C_TDIC show very large ranges from 4.6 to 145.3 mmol/Kg and from –10.0‰ and 2.8‰, respectively. Calculated values indicate the significant contribution from a deep source of carbon dioxide inorganic in origin. Interaction with Mediterranean magmatic CO₂ characterized by heavier carbon isotope ratios ( value from -3 to 0‰ vs V-PDB (CAPASSO et al., 1997, GIAMMANCO et al., 1998; INGUAGGIATO et al., 2000) with respect to MORB value and/or input of CO₂-derived from thermal decomposition of marine carbonates have been inferred.     

Determination of source duration and moment of earthquakes in the Indian Peninsula using love waveforms

Love waves recorded by a long-period seismograph at New Delhi (NDI) from seven earthquakes of magnitude 4.3 to 5.2 in Koyna and Bhatsa on the western coast and one earthquake in Ongole on the eastern coast of the Indian Peninsula have been used to determine the seismic moment for each of the earthquakes by waveform modeling. Transverse component of the synthetic seismogram shows that the maximum amplitude of waveform decreases with an increase of source duration. Thus for an evaluation of the seismic moment by equating the amplitude level of the observed and synthetic waveforms, we must know the source duration. The synthetic seismogram also indicates that a short source duration gives rise to a small but sharp pulse and this pulse is interpreted as anLg wave. Comparison of the observed and synthetic waveforms has been used for a simultaneous evaluation of the source duration and seismic moment. The source durations are found to vary between 2.2 and 4.4 s; for earthquakes with a magnitude range between 4.3 and 5.2 these durations are slightly higher than normal. We obtain moment (M ₀) of Ongole earthquake (M _L =5.1)as 1.7×10²⁴ dyne-cm; moments of Koyna and Bhatsa earthquakes (4.3M _L 5.2) on the western coast lie between 0.7×10²³ and 3.6×10²³ dyne-cm. Moment (M ₀)-magnitude (M _L ) relation logM ₀=1.5M _L +16.0 for the western United States region agrees as well, in general, with the results for the earthquakes in the Indian Peninsula.     

The source and fate of sediment and mercury in Hunza River basin,Northern Areas,Pakistan

This article presents results of mercury in surface waters from Hunza River basin, Northern Areas, Pakistan. Small‐scale gold mining activities along the Hunza and Gilgit rivers are long known to be discharging mercury in the amalgamation and roasting processes. Previous studies reported high mercury concentrations in soils close to mining operations as well as serious health problems for miners. However, none of the studies have focused on the level of contamination in aqueous environments. This is the first study on the investigation of source and fate of sediment and river‐borne mercury in the Hunza River. The samples collected near gold panning sites showed higher mercury concentrations than critical levels established by the U.S. Environmental Protection Agency. The observed dissolved mercury concentrations ranged from 5.10 to 25.25 ng/l, whereas particulate‐bound mercury ranged from 4.85 to 154.62 ng/l. Particulate‐phase mercury corresponded to more than 75% of the total observed mercury concentrations for all of the sampled rivers. Thus, suspended sediments represented the major pathway of the riverine mercury transport. A mass balance calculation suggested an annual mercury flux of 48.6 g/km² into the Hunza River basin. The samples collected from the most affected river, the Shimsal River, averaged to have 108 ng/l total mercury. This amount was close to the average soil mercury data of 151 ng/l as reported by the Pakistan Mineral Development Corporation in 2001. The dominant source of contamination was shown to be the leaching of large quantities of mercury from the mercury‐rich sediment and flood plain soil into the rivers, rather than the direct release from mining activities. Significant decrease in both dissolved and particulate‐bound mercury concentration downstream of Attabad Lake suggested that mercury is being accumulated or consumed in the lake. Although minimization or elimination of mercury loses from the mining process seems important for the well‐being of the miners, preventing the remobilization of accumulated mercury is equally important in mercury control in this region. Copyright © 2014 John Wiley & Sons, Ltd.     

Hysteresis‐based analysis of overland metal transport

Introducing a concept of equivalent mass depth of flow, this study describes the phenomenon of non‐point source pollutant (metal) transport for pavement (or overland) flow in analogy with wave propagation in wide open channels. Hysteretic and normal mass rating curves are developed for runoff rate and mass of 12 dissolved and particulate‐bound metal elements (pollutants) using the rainfall‐runoff and water quality data of the 15 × 20 m² instrumented pavement in Cincinnati, USA. Normal mass rating curves developed for easy computation of pollutant load are found to be of a form similar to Manning's, which is valid for open channel flows. Based on the hysteresis analysis, wave types for dissolution and mixing of particulate‐bound metals are identified. The analysis finds that the second‐order partial‐differential equation normally used for metal transport does not have the efficacy to describe fully the strong non‐linear phenomena such as is described for various metal elements by dynamic waves. In addition, the proportionality concept of the popular SCS‐CN concept is extended for determining the potential maximum metal mass M_p of all the 12 elements transported by a rain storm and related to the antecedent dry period (ADP). For the primary metal zinc element, M_p is found to increase with the ADP and vice versa. Copyright © 2003 John Wiley & Sons, Ltd.     

Interaction of trace metals with natural particle surfaces: Comparison between adsorption experiments and field measurements

The distribution of the metal ions Zn and Pb between particulate and dissolved phase in river Glatt was studied by field measurements and compared with calculated simulations, using parameters obtained by adsorption experiments with natural suspended particulate material. Differences in distribution coefficients obtained from field data are observed in function of the sampling locations and of the composition of the particulate matter.Experiments in which metal ion solutions are titrated with a suspension of natural particles and analyzed by anodic stripping voltammetry, are interpreted in terms of binding capacities and conditional stability constants of Zn and Pb with the surface sites. Binding constants of a particular metal ion varied very little for all samples. We obtained mean values for the conditional average complex formation constants at pH 8 of: log^cond K _Pb = 9.44 ± 0.18 and log^cond K _Zn = 8.17 ± 0.20. At this pH, binding capacities of 5 10^–3 – 1.7 10^–2 mol/kg of particles were obtained for samples collected at different locations and times; organic material, iron and manganese oxides are considered to be the main components that control the adsorption to the particles.Distribution coefficients are calculated from the experimentally obtained binding capacities and conditional stability constants. Calculated distribution coefficients for Zn agree with those obtained from the field data and are not very sensitive to changes in the composition of the solution. Good agreement was obtained for lead as well; for some samples it was important to take two types of sites with different affinity into consideration.     

Distribution and fluxes of metals in the St. Lawrence River from the outflow of Lake Ontario to Québec City

Six anchor stations in the St. Lawrence River from the outflow of Lake Ontario to Quebec City, were occupied for ca. 24 hours in June 1987 during low flow conditions. Samples of water and suspended particulate matter were separated by continuous-flow centrifugation, and were collected every two hours.During this sampling period, fluxes of dissolved forms of zinc, copper and nickel increased in Lac St. François and downstream relative to the sum of the fluxes for the two upstream stations at the outflow of Lake Ontario. Increases in the flux of dissolved zinc and copper were pronounced below Montreal and above Lac St. Pierre. For particulate forms of metals, all five metals show that there are significant inputs in the section of the St. Lawrence River between Lac St. François and the station just above the entrance to Lac St. Pierre.The average concentrations of dissolved cadmium, lead, zinc, copper and nickel ranged from 7–23 ng/l; 9–35 ng/l; 0.434–0.939 g/l; 0.15–0.89 g/l and 0.58–1.12 g/l respectively.Regression analysis of the dissolved and particulate metal concentrations suggests that the concentration of dissolved cadmium, lead, zinc and nickel can be predicted from the regression equation and the determination of particulate metal concentration. This prediction appears to be independent of the suspended particulate matter concentration which varies from ca. 1 to 10 mg/l from the outflow of Lake Ontario to Québec City.     

Aerial flux of particulate hydrocarbons to the Chesapeake Bay Estuary

Bulk hydrocarbon deposition rates have been measured over a 15 month period at four stations in south-eastern Virginia surrounding the lower Chesapeake Bay. A nearly linear trend of atmospheric particulate deposition was recorded. Deposition rates at the urban station (195 μg m^?2 day^?1) were aproximately three times greater than those recorded for nonurban and coastal locations (mean value 69 μg m^?2 day^?1). The increased levels at the urban location were attributed to localized source inputs. Anthropogenic hydrocarbons accounted for approximately 50% of the total deposition at all stations. Significant biogenic inputs were indicated by the odd/even n-alkane distribution. A minimum flux to the water surface, based on mean nonurban deposition rates (24 mg yr^?1), indicated an annual particulate hydrocarbon flux of +275 metric tons. Little information is available for the comparison of additional source inputs; however, the data reported here indicate that the aerial deposition of hydrocarbons is of the same order of magnitude as the input from municipal wastewater facilities and accidental discharge and is a potentially significant source of hydrocarbon pollution to the Chesapeake Bay Estuary.     

River flux uncertainties predicted by hydrological variability and riverine material behaviour

Data on riverine fluxes are essential for calculating element cycles (carbon, nutrients, pollutants) and erosion rates from regional to global scales. At most water‐quality stations throughout the world, riverine fluxes are calculated from continuous flow data (q) and discrete concentration data (C), the latter being the main cause of sometimes large uncertainties. This article offers a comprehensive approach for predicting the magnitude of these uncertainties for water‐quality stations in medium to large basins (drainage basin area > 1000 km²) based on the commonly used discharge‐weighted method. Uncertainty levels – biases and imprecisions – for sampling intervals of 3 to 60 days are correlated first through a nomograph with a flux variability indicator, the quantity of riverine material discharged in 2% of time (M_2%). In turn, M_2% is estimated from the combination of a hydrological reactivity index, W_2% (the cumulative flow volume discharged during the upper 2% of highest daily flow) and the truncated b_50sup exponent, quantifying the concentration versus discharge relationship for the upper half of flow values (C = a q ^b50sup, for q > q₅₀, where q₅₀ is the median flow): M_2% = W_2% + 27.6b_50sup. W_2% can be calculated from continuous flow measurements, and the b_50sup indicator can be calculated from infrequent sampling, which makes it possible to predict a priori the level of uncertainty at any station, for any type of riverine material either concentrated (b_50sup > 0) or diluted (b_50sup > 0) with flow. A large data base of daily surveys, 125 station variables of suspended particulate matter (SPM), total dissolved solids (TDS) and dissolved and particulate nutrients, was used to determine uncertainties from simulated discrete surveys and to establish relationships between indicators. Results show, for example, that for the same relatively reactive basin (W_2% > 25%), calculated fluxes from monthly sampling would yield uncertainties approaching ±100% for SPM (b_50sup > 1.4) fluxes and ±10% for TDS (b_50sup = ?0.2). The application to the nitrate survey of the river Seine shows significant trends for the 1972–2009 records. Copyright © 2012 John Wiley & Sons, Ltd.     

Barium and radium in the Dead Sea

We have measured Ba in Dead Sea samples collected before and after the 1979 overturn, and²²⁶Ra in nine samples collected after the overturn. Before this overturn, Ba and the²²⁶Ra data measured by Chung and Craig [4] show that a distinct two-layer structure existed, with higher concentrations in the upper layer. After the overturn, both elements were uniformly distributed in the water column. The inventories of Ba and Ra calculated from these data are the same for the periods before and after the overturn. If the inventories were constant during the last meromictic phase then the input rate must be balanced by the removal rate, and a mass balance model can be constructed to estimate physical parameters based on known or deduced sources and sinks. The sources include inputs from the Jordan River, springs around the Dead Sea, and submerged springs or seepages, etc. The sinks include coprecipitation with aragonite, gypsum, precipitation of barite, coprecipitation of Ra with barite, particulate scavenging, and radioactive decay for Ra. Our data include measurements of Ba and²²⁶Ra in gypsum, aragonite and halite from the Dead Sea, as well as in some of the inflowing rivers and springs.The inclusion of particulate scavenging as a sink is a major element of the model. We find that, without inclusion of a Ba scavenging term in the deep water, the lake volume at the previous overturn as calculated from the Ba data would be unrealistically high in comparison with historical records. The inclusion of particulate scavenging for Ra in the model reduces the calculated duration of the last meromictic phase significantly.Our model excludes internal mixing between the upper and lower water masses. With this restriction, various sets of model parameters were calculated as a function of theRa/Ba scavenging rate ratio. If the ratio is one, the calculated age of the last meromictic phase is about a hundred years. A substantial increase in the Ra input rate is required to balance the removal rate by particulate scavenging as well as decay. If the ratio is zero, i.e. no particulate scavenging for Ra, the age is about 260 years, as obtained by Stiller and Chung [2].