Sampling frequency and accuracy of SPM flux estimates in two contrasted drainage basins

The present paper is based on discharges and suspended particulate matter concentrations from a 9-years high-resolution database for the Garonne River (large plain river) covering contrasted hydrologic years, and a 12-months high frequency sampling for the Nivelle River (small mountainous river). Annual SPM fluxes in the Garonne River range from 0.6 x 10(6) t year(-1) (1997) to 3.9 x 10(6) t year(-1) (1996). In contrast, the Nivelle River transported 11 x 10(3) t year(-1) from December 1995 to December 1996. From the long-term observation of the Garonne River an empirical relation between SPM* (discharge-weighted mean annual SPM concentrations) and annual discharge was established. This relation allows estimating annual SPM fluxes for the Garonne River with less than 30% deviation from reference values for the whole range of mean annual discharge observed during the past decade. Specific (=area-normalized) annual SPM fluxes (YSPM) range from 11 to 74 t km(-2) year(-1) for the Garonne River. Comparison of these results with YSPM of the Nivelle River (69 t km(-2) year(-1) in 1996) suggests that interannual hydrological variations may have a greater impact on fluvial SPM transport than basin-specific parameters. By extracting individual SPM concentrations and corresponding discharge values from the database, different sampling frequencies were simulated and resulting SPM fluxes were then compared to reference fluxes derived from the complete database. If a deviation of simulated flux estimates from reference fluxes lower than +/-20% is accepted, the Garonne River (large plain river) must be sampled at least every 3 days (10 samples per month) and the Nivelle River every 7 h (approx. 100 samples per month). For the Garonne River this minimum sampling frequency is valid for all contrasted hydrologic years of the observation period. Below these minimum sampling frequencies, annual SPM flux estimates may greatly differ from reference fluxes (up to 200%) and there is high probability of systematic underestimation. Consequently, annual SPM flux estimates for the Garonne River derived from the empirical relation (SPM*-annual discharge) are likely to be more satisfactory (errors <30%) than estimates based on sampling frequencies lower than the minimum frequency. These findings underline the need of adapted sampling strategies for erosion assessment, reliable chemical (e.g. nutrients and pollutants) mass balances and characterisation of fluvial transport mechanisms in the world's contrasted watersheds.     

Modeling nitrate fluxes at the catchment scale using the integrated tool CAWAQS

Nitrates fluxes in the Grand Morin basin (1200 km(2)), that is subjected to intense agricultural pressure, are considered using in-stream observations (around 250 sampling days over 5 years) and physically based simulations using the CAWAQS model (CAtchment WAter Quality Simulator). In-stream nitrate concentration averaged 6 mg N L(-1), increasing by approximately 0.2 mg N L(-1) yr(-1) around this value (period 1991-1996). Our results show that, over the period of 1991-1996, the differences between in-stream observed nitrate concentrations and simulated nitrate concentrations result from nitrate losses at the basin scale. These losses are due to denitrification by transfer through wetlands, alluvial plains, the hyporheic zone, and by benthic processes in rivers. A mean annual mass balance at the basin scale indicates that 40% of the infiltration flux (3360 kg N km(-2) yr(-1)) is removed from the system via the river network, 40% is stored in aquifers and 20% is lost by denitrification (period 1991-1996).     

Relationship between ore deposits in river catchments and geochemistry of suspended particulate matter from six rivers in southwest France

Here we present original data on the geochemical composition of fluvial particulate matter transported by the rivers of the Adour/Garonne basin, which drains one-fifth of the French land surface. Suspended particulate matter from the six main rivers in the basin, sampled at 'normal' flow and during a flood, is compared in terms of: grain size; particulate organic carbon; Fe; Mn; and trace element concentrations (e.g. Zn, Cd, Pb, Cu, Mo, Sn, Ni, Co, Cr, V, As, Hg, U, Th, W, Au, Ag, Ta). Three of the six studied rivers (Garonne, Dordogne and Isle Rivers) are the main tributaries of the Gironde estuary (southwest France), known for Cd pollution. The Adour and Gaves Rivers enter the Adour Estuary and the Charente River reaches the ocean by the Charente Estuary. Our data show, that Cd (and Zn) are not the only trace elements of eco-toxicological relevance transported into the Gulf of Biscay by these six rivers. Potentially toxic elements (e.g. As, Sn, U, Cu, Ag) show elevated concentrations in river particulates entering the estuaries, compared to world average concentrations [Martin and Whitfield, 1983, The significance of the river input of chemical elements to the oceans. In: C.S. Wong, E. Boyle, K.W. Bruland, J.D. Burton, E.D. Goldberg (editors), Trace Metals in Sea Water, Plenum, New York: pp. 265-296]. Comparing SPM sampled during 'normal' discharge and flood, the basin shows a distinct trace element composition of SPM mostly related to ore deposits in the upper basins (Massif Central and Pyreneans). This geochemical signal is partly masked during floods due to changes in grain size, but also due to increased erosion of the lower parts of the basins. This study proves pumping/centrifugation to be the most appropriate sampling/separation technique (recovery, representativity, contamination) by comparing different methods of SPM recovery.     

Critical budget of metal sources and pathways in the Seine River basin (1994-2003) for Cd, Cr, Cu, Hg, Ni, Pb and Zn

River basin metal pollution originates from heavy industries (plating, automobile) and from urban sources (Paris conurbation: 2740 km(2), 9.47 million inhabitants). The natural sources of metal have been found to be limited due to sedimentary nature of this catchment and to the very low river sediment transport (10 t km(-2) y(-1)). Several types of data have been collected to build the metal budget within the whole Seine River basin: field surveys, economical statistics and environmental models. Environmental contamination and related fluxes have been measured on atmospheric fallout, rural streams particles, and Seine River particles upstream and downstream of Paris and at river mouth. Metal pathways and budgets have been set up for (i) a typical cultivated area, (ii) a Paris combined sewer system, (iii) Paris conurbation and (iv) the whole catchment metal retention effect in floodplain and dredged material. Metal fluxes to the estuary have been decomposed into natural, urban domestic and other sources. The latter are within 1-2 orders of magnitude larger than waste water fluxes directly released into rivers according to an industrial census. These fluxes have been further compared to the annual use (1994-2003) of these metals. Metal excess fluxes exported by the river are now a marginal leak of metal inputs to the catchment (i.e. "raw" metals, metals in goods, atmospheric fallout), generally from 0.2 to 5 per thousand. However, due to the very limited dilution power in this basin, the contamination of particles is still relatively high. The Seine River basin is gradually storing metals, mostly in manufactured products used in construction, but also in various waste dumps, industrial soils, agricultural and flood plain soils.     

Mass balance for polycyclic aromatic hydrocarbons in the urban watershed of Le Havre (France): transport and fate of PAHs from the atmosphere to the outlet

Polycyclic aromatic hydrocarbon (PAH) concentrations have been monitored simultaneously in ambient air, bulk atmospheric deposition and runoff waters during one year in a small urban watershed of the Seine river basin (France). PAH fluxes from the atmosphere to the outlet of the urban watershed have been calculated to establish a mass balance for PAHs. PAH flux in runoff waters was 5.2 kg km(-2) yr(-1) while PAH atmospheric deposition was 0.21 kg km(-2) yr(-1). The comparison between atmospheric input and output by runoff has shown the importance of street deposits that appeared to be the most important source of PAHs for surface waters in urban areas. PAH profiles in the various compartments showed the fate of PAHs in the air-water system: proportion of carcinogenic PAHs was more important in runoff waters (35%) than in bulk atmospheric deposition (22%) and air (6%).     

Contribution of a medium-sized tropical river to the particulate heavy-metal load for the South Atlantic Ocean

The Paraíba do Sul River is a medium-sized river, 1145 km in length with a drainage basin of 55,400 km2. The riverine fluxes of particulate metals (Cu, Cr, Zn, Mn and Fe) were investigated over 24 months. Particulate matter samples were monthly collected from April 1994 to March 1996. The first 12-month period presented lower rainfall than the second, although both periods presented average precipitation lower than the regional average. The particulate matter flux in the second period (2,042,080 t) was 250% higher than the first period (821,489 t). The same trend was observed for the associated metals, which presented higher fluxes in the second period. This study highlights the strong dependence of the transported mass on the rainfall, and consequently with the river water discharge. The Paraiba do Sul River presents a low contribution to the world oceans, although the local contribution could be considered relevant.     

Hydrochemistry and mercury cycling in a High Arctic watershed

Mass budgets for total mercury, major ions and nutrients were calculated for Amituk Lake, located on Cornwallis Island, Nunavut, Canada. Total mercury in two distinct snowpacks averaged 1.25 and 4.21 ng L(-1); the discharge-weighted concentration of influent streams averaged 0.76 ng L(-1). The recent and pre-industrial Hg(T) fluxes in atmospheric deposition to the catchment were estimated to be 0.57 and 0.23 microg m(-2) but through retention within the catchment and/or re-volatilization from the melting snowpack, these decreased by 69% in the lake inflow. The spring freshet was the prime conduit for transporting Hg(T) into Amituk Lake. Because of limited mixing of surface runoff with the lake water column during snowmelt, 59% of the Hg(T) input was directly discharged through the outflow, 16% entered the lake water column where concentrations increased from 0.23 to 0.33 ng L(-1) from June to August and 25% was deposited to the bottom sediments producing a sediment Hg(T) flux of 3.1 microg m(-2).     

Seasonal variations and annual fluxes of arsenic in the Garonne, Dordogne and Isle Rivers, France

Daily measurements of water discharges and suspended particulate matter (SPM) concentrations and monthly analyses for arsenic were conducted from 1999 to 2005 on the Garonne, Dordogne and Isle Rivers, the three main tributaries of the Gironde Estuary, France. Despite the known historical polymetallic pollution affecting the Lot-Garonne River system, the highest As concentration level was observed in the Isle River. This was explained by the geological context and various Au/As deposits in this watershed. In the three studied rivers, dissolved As concentrations showed important seasonal variations with maximum values in summer. The dissolved As concentrations were closely related to water temperature and their increase in spring/summer appeared to be induced by water temperatures above approximately 15 degrees C, independently from discharge. The reduction of As(V) to more soluble As(III) and/or destruction of solid As carrier phases by micro-organisms could explain this observation, suggesting that temperature-dependent biogeochemical processes play an important role in controlling As partition and speciation in fluvial systems. Water and SPM fluxes in the Garonne River mainly control arsenic inputs into the Gironde Estuary and the downstream coastal zones. Based on the present data, we propose an empirical model to roughly estimate the annual dissolved and particulate As fluxes in the Garonne, Dordogne and Isle Rivers from annual water and SPM fluxes. The comparison of observed As fluxes and those estimated from the empirical model suggests that resuspension of historical, polluted reservoir sediments during a major flood accounted for approximately 50% of the annual As fluxes in 2003.     

Long-term monitoring (1960-2008) of the river-sediment transport in the Red River Watershed (Vietnam): Temporal variability and dam-reservoir impact

The Red River (China/Vietnam, A = 155,000 km²) is a typical humid tropics river originating from the mountainous area of Yunnan Province in China. Based on information on daily discharge (Q) and suspended particulate matter (SPM) concentration between 1960-2008 for the SonTay gauging station (outlet of the River and entry to the Delta) provided by the National Institute IMHE-MONRE, the mean annual SPM flux was estimated at 90 Mt/yr, corresponding to a sediment yield of 600 t/km²/yr. The temporal variability of annual SPM fluxes (ranging from 24 to 200 Mt/yr) is strongly related to the interannual hydrological conditions. However, some years of high water flow were not associated with high sediment fluxes, especially after 1989 when the HoaBinh dam came into operation. Therefore, the median discharge pre- (3389 m³/s) and post 1989 (3495 m³/s) are similar indicating there was little or no change between both periods. Sediment rating curves (power law-type; SPM = aQ^b) were fitted for both periods (1960-1989; 1990-2008). The analysis of the pre- and post-1989 sediment rating parameters (a, b) suggests a downshift of b-parameter values after 1989, attributed to a decrease of the sediment supply due to the commissioning of the HoaBinh dam. A single sediment rating curve derived from 1960-1989 data was used to simulate the annual variability of former sediment delivery, generating excellent cumulative flux estimates (error ~ 1%). In contrast, applying the same rating curve to the 1990-2008 data resulted in systematic and substantial (up to 109%) overestimation. This suggests that the HoaBinh dam reduces annual SPM delivery to the delta by half, implying important metal/metalloid storage behind the HoaBinh dam.     

Groundwater contributions to metal transport in a small river affected by mining and smelting waste

The Riou Mort watershed, strongly affected by former coal mining and Zn ore treatment, has been the major source of the historical polymetallic pollution of the Lot-Garonne-Gironde fluvial-estuarine system. Two decades after the end of ore treatment, the former industrial area still contributes important amounts of metals/metalloids from various, partly unidentified, sources to the downstream river system. This study presents the high spatial variability of metal/metalloid (Cd, Zn, As, Sb, U, V) concentrations in water and suspended particulate matter (SPM) from eight observation sites during a short, intense flood event. Despite important dilution effects, the observed concentration levels at the different sites suggested additional Cd and Zn inputs, probably from polluted groundwater. This formerly unknown metal source was then localized and characterized by sampling water and SPM along two longitudinal profiles during different hydrological situations. Groundwater inputs of "truly dissolved" (<0.02 microm) Cd and Zn occurred along approximately 200 m, contributing 43% and 28% to the total annual (2004) Cd and Zn fluxes in the Riou Mort River. The estimated groundwater concentrations of Cd and Zn (2500-6700 and 83,000-170,000 microg l(-1), respectively) in the source zone were consistent with values measured in samples from the near aquifer (5400-13,000 and 200,000-400,000 microg l(-1)). The present work induced concrete remediation actions (pumping and treatment of the polluted groundwater), that are expected to strongly reduce dissolved Cd and Zn emissions into the Riou Mort River.     

Dissolved and particulate nutrient export from rural catchments: a case study from Luxembourg

Nutrient enrichment of freshwaters continues to be one of the most serious problems facing the management of surface waters. Effective remediation/conservation measures require accurate qualitative and quantitative knowledge of nutrient sources, transport mechanisms, transformations and annual dynamics of different nitrogen (N) and phosphorus (P) forms. In this paper, nitrate (NO3-N), soluble reactive phosphorus (SRP) and total phosphorus (TP) concentrations and loads are presented for two adjacent rural basins of 306 km2 and 424 km2, and for five sub-basins differing in size (between 1 km2 and 33 km2), land use (extent of forest cover between 20% and 93%) and household pressure (from 0 to 40 people/km2) with the aim of studying the influence of land use and catchment size on nutrient exports. The studied catchments are all situated on Devonian schistous substrates in the Ardennes region (Belgium-Luxembourg), and therefore have similar hydrological regimes. As the study period could not be the same for all basins, annual export coefficients were corrected with the 25 years normalized discharge of the Sure River: two regression analyses (for dry and humid periods) relating monthly nutrient loads to monthly runoff were used to determine correction factors to be applied to each parameter and each basin. This procedure allows for the comparing annual export coefficients from basins sampled in different years. Results show a marked seasonal response and a large variability of NO3-N export loads between forested (4 kg N ha-1 year-1), agricultural (27-33 kg N ha-1 year-1) and mixed catchments (17-22 kg N ha-1 year-1). For SRP and TP, no significant agricultural impact was found. Land and bank erosion control the total P massflow in the studied catchments (0.4-1.3 kg P ha-1 year-1), which is mostly in a particulate form, detached and transported during storm events. Soluble reactive P fluxes ranged between 10% and 30% of the TP mass, depending on the importance of point sources in the basins studied. No relation was found between the size of the basins and the export of nitrate, SRP or TP. Nutrient export, specially for NO3-N and TP, shows significant inter-annual variations, closely linked to inter-annual discharge variations. Flow and load frequency data analysis confirm this association for all the basins on an annual basis. Seasonal or storm specific fluxes strongly deviate from their annual values.     

Retrieval of suspended particulate matter concentrations in the Danube River from Landsat ETM data

Alternations in river channel morphology result in a disturbed natural transport of suspended particulate matter (SPM). Suspended particulate matter serves as a transport medium for various pollutants, e.g. heavy metals. It is therefore important to understand how artificial obstructions alter the natural transport of suspended matter. Measurements of SPM in rivers are traditionally carried out during in situ sampling campaigns, which can provide only a limited view of the actual spatial distribution of suspended matter over large distances. Several authors have studied how space-borne remote sensing could be used for mapping of water quality in standing waters, but with only little attention paid to rivers. This paper describes the methodology how a Landsat ETM image was used to map the spatial patterns of SPM in the Slovak portion of the Danube River. Results of our investigation reveal that the Danube River in Slovakia exhibits gradual longitudinal decrease in concentrations of SPM. Based on a strong relationship between the Landsat near-infrared band (TM4) and field measurements, we developed a map of suspended particulate matter in the Danube River with a standard error (SE) of 2.92 mg/L. This study aims to show how archived satellite data and historical water quality data can be used for monitoring of SPM in large rivers. A methodology describing the minimum samples required for sufficiently accurate results is discussed in this paper also.     

Distribution of 7Be, 210Pb and 137Cs in watersheds of different scales in the Seine River basin: inventories and residence times

The activity of environmental radionuclides ((7)Be, (210)Pb and (137)Cs) was monitored in nested catchments, inside the Seine River basin. Suspended matter data was collected at 8 different watersheds, ranging from order 1 to order 7, and ranging in size over 4 orders of magnitude. Suspended matter was analyzed for (210)Pb, (137)Cs and (7)Be, and used to calculate the flux of sediments out of each watershed. Monthly atmospheric flux data of (210)Pb and (7)Be was analyzed to assess the input flux of each into the watersheds, taking into account the rainfall during sampling periods. Taking advantage of the different half-lives of (7)Be (53 days) and (210)Pb (22 years), a two-box model was built for each of the catchments following a methodology previously developed by Dominik et al. [Dominik J, Burrus D, Vernet JP. Transport of the environmental radionuclides in alpine watershed. Earth Planet Sci Letters 1987; 84: 165-180.]. The model divides the watershed into a soil box and a rapid reservoir and provides insight into the removal rate of suspended matter from the surrounding watershed. The model enables the assessment of the surface area and the residence time of slow and rapid reservoirs to describe the fate of contaminants of atmospheric origin inside the river basin. The model was improved by considering the dissolved fraction in the total flux and adding the (137)Cs inventory as an additional constraint. The effects of these changes are discussed. Residence times in the soil box, characterized by low transport velocity, range between 4800 years at Melarchez (order 1) to about 30000 years at Andresy and Poses (order 7). They remain constant in each watershed over a large range of variation of atmospheric fluxes of (7)Be and (210)Pb during the whole study, but are sensitive to SM variations. The residence time in the rapid box, which includes the surface of the river and immediate surroundings, is less than one year, while its surface area is in the range 0.6% to 2.2% of the total catchment area. They are sensitive to (7)Be atmospheric flux variations. The two-box model was used to estimate the amount of the radionuclides in each reservoir. Inventories appear to be constant from one watershed to the next. The (7)Be inventory ratio in the rapid and slow boxes expresses the rate of particle-reactive atmospheric pollutants that will be rapidly delivered to the river.     

Land inputs of trace metals, major elements, particulate organic carbon and suspended solids to an industrial coastal bay of the NE Atlantic

Rivers, streams and municipal and industrial effluents flowing into the Ferrol Ria (NW Spain) were analyzed for dissolved and particulate trace elements (Cd, Cu, Pb, Zn), particulate major elements (Al, Fe, Si), particulate organic carbon and nitrogen (POC and PON), and total suspended solids. Trace metal clean techniques were applied. Mean annual fluxes of these components were calculated. Dissolved trace metal concentrations in the major freshwater inputs were found to be within typical values for uncontaminated rivers: Cd: 0.020-0.035 nM; Cu: 11.7-19.2 nM; Pb: 0.40-0.71 nM and Zn: 18-54 nM. Two sources of suspended particulate matter (SPM) were observed: (i) a detrital SPM, which becomes more important at high river discharges, with metal concentrations tending to lithogenic values; (ii) an organic- and metal-rich SPM, which becomes dominant at low discharges. Municipal and industrial effluents in the northern shore, despite of constitute a minor freshwater contribution to the bay, were responsible for more than 50% of total inputs of Cu, Cd, Pb, Zn, POC and PON. The fluxes of trace metals obtained for the Ferrol Ria are in the range of other inhabited world semi-enclosed embayments.     

Downward fluxes of particulate carbon, nitrogen and phosphorus in the north-western Adriatic sea

Downward fluxes of particles, organic carbon, total nitrogen and total phosphorus and the composition of the settled particulate matter were determined in the north-western Adriatic Sea at two coastal sites influenced by the outflows of the Po and Adige rivers and one offshore site. Vertical fluxes were strongly influenced by resuspension processes in addition to the primary flux and advection. The resuspended material contributed on average 34-43% of the total matter sedimented in the near bottom traps in coastal waters. Net annual vertical fluxes (due to primary flux and advection) of organic carbon, total nitrogen and phosphorus in the coastal stations were: 71-97 g C m(-2) year(-1), 8-14 g N m(-2) year(-1) and 2.1-2.3 g P m(-2) year(-1), with the highest values recorded at the station off the Po river delta. The offshore site was characterised by net annual fluxes of particulates, C, N and P approximately one order of magnitude lower than the above. The carbon export to the bottom was limited in the warm seasons when it constituted only 2-9% of primary production, due to high recycling and utilisation in the upper layer of the water column, increasing up to 8-18% in winter because of the instability of the water column and low biological utilisation.     

Characterisation of urban catchment suspended particulate matter (Auckland region, New Zealand); a comparison with non-urban SPM

Suspended particulate matter (SPM) is an important transport agent for metal contaminants in streams, particularly during high flow periods such as storm events. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal partitioning between the dissolved phase and SPM was determined, and SPM characterised in terms of its Si, Al, Fe, Mn, Zn, Cu, Pb, TOC, TON and PO(4) concentrations, as well as particle size, abundance, type and surface area. This data was compared to similar data from representative non-urban catchments in the Auckland region, the Kaipara River and Waikato River catchments, to identify any significant differences in the SPM and its potential trace metal adsorption capacity. Trace metal partitioning was assessed by way of a distribution coefficient: K(D)=[Me(SPM)]/[Me(DISS)]. Auckland urban SPM comprises quartz, feldspars and clay minerals, with Fe-oxides and minor Mn-oxides. No particles of anthropogenic origin, other than glass shards, were observed. No change in urban SPM particle size or SSA was observed with seasonal change in temperature, but the nature of the SPM was observed to change with flow regime. The abundance of finer particles, SSA and Al content of the SPM increased under moderate flow conditions; however, Si/Al ratios remained constant, confirming the importance of aluminosilicate detrital minerals in surface run-off. The SPM Fe content was observed to decrease with increased flow and was attributed to dilution of SPM Fe-oxide of groundwater origin. The Kaipara River SPM was found to be mineralogically, chemically and biologically similar to the urban SPM. However, major differences between urban catchment SPM and SPM from the much larger (non-urban) Waikato River were observed, and attributed to a higher abundance of diatoms. The Fe content of the Waikato River SPM was consistently lower (<5%), and the Si/Al ratio and Mn content was higher. Such differences observed between urban and non-urban SPM did not appear to affect the partitioning of Zn and Cu; however, Pb in the Kaipara and Waikato Rivers was found to be more associated with the dissolved phase. This is likely to reflect higher particulate Pb inputs to urban systems.     

Probing Hg evasion from surface waters of two Chinese hyper/meso-eutrophic reservoirs

Measurements of water/air exchange flux of gaseous elemental mercury (GEM) were conducted in a hyper-eutrophic reservoir and a meso-eutrophic reservoir in southwest China in both warm and cold seasons by using a dynamic flux chamber (DFC) method coupled with an automatic gaseous Hg analyzer. Both strong diurnal and seasonal variations of GEM fluxes were observed. The diurnal cycle of the GEM flux was more pronounced during sunny days compared to cloudy and rainy days, which highlights the effect of solar intensity on the GEM flux. GEM fluxes in warm seasons were considerably higher (2.5 to 4.1 times higher) than in cold seasons, which was attributed to the combined factors including meteorological factors, water quality parameters and water Hg concentrations. Clear variation in GEM fluxes was observed between the two reservoirs. Mean GEM fluxes in the hyper-eutrophic reservoir (WJD) (3.2-20.1 ng m⁻² h⁻¹) were significantly higher than those in the meso-eutrophic reservoir (SFY) (0.6-4.4 ng m⁻² h⁻¹). Evasion of Hg played a distinct role in the mass balance of Hg in the two reservoirs. In WJD, evasion was the second most important mechanism for Hg losses from the reservoir (17.5% of the total losses); whereas in SFY, loss of Hg via volatilization constituted an extremely little portion to the total losses of Hg (0.8%).     

Elemental gaseous mercury flux at the water/air interface over the Negro River basin, Amazon, Brazil

The amount of dissolved gaseous mercury (DGM) released annually into the atmosphere by water bodies in each of the 18 major sub-basins of the Negro River tributaries has been estimated for the wet season and adopted for the entire year. Using Remote Sensors (RS) and the Geographic Information System (GIS), an estimate was made for the total flooded area during the period of the wet season (May-July), which corresponds to around 10% of the total basin area. The estimates of DGM evasive flux values were made during four scientific campaigns and ranged from 0.09 to 14 mug m(-2) y(-1). Mercury wet deposition to the same area was estimated using average values of the metal concentration in the rainwater (9.8 ng L(-1)), which varies from 17 to 27 microg m(-2) year(-1). Considering the flooded area of the Negro River Basin as 69,000 km(2), the total amount of mercury emitted by all bodies of water reaches nearly 0.26 ton year(-1), which represents not more than 2% of the total mercury found in wet deposition in this same area.     

Gully hotspot contribution to landscape methane (CH4) and carbon dioxide (CO2) fluxes in a northern peatland

Peatlands are long term carbon catchments that sink atmospheric carbon dioxide (CO(2)) and source methane (CH(4)). In the uplands of the United Kingdom ombrotrophic blanket peatlands commonly exist within Calluna vulgaris (L.) dominated moorland ecosystems. These landscapes contain a range of topographical features that influence local hydrology, climate and plant community composition. In this study we examined the variation in ecosystem CO(2) respiration and net CH(4) fluxes from typical plant-soil systems in dendritic drainage gullies and adjacent blanket peat during the growing season. Typically, Eriophorum spp., Sphagnum spp. and mixed grasses occupied gullies while C. vulgaris dominated in adjacent blanket peat. Gross CO(2) respiration was highest in the areas of Eriophorum spp. (650+/-140 mg CO(2) m(-2) h(-1)) compared to those with Sphagnum spp. (338+/-49 mg CO(2) m(-2) h(-1)), mixed grasses (342+/-91 mg CO(2) m(-2) h(-1)) and C. vulgaris (174+/-63 mg CO(2) m(-2) h(-1)). Measurements of the net CH(4) flux showed higher fluxes from the Eriophorum spp (2.2+/-0.6 mg CH(4) m(-2) h(-1)) locations compared to the Sphagnum spp. (0.6+/-0.4 mg CH(4) m(-2) h(-1)), mixed grasses (0.1+/-0.1 mg CH(4) m(-2) h(-1)) and a negligible flux detected from C. vulgaris (0.0+/-0.0 mg CH(4) m(-2) h(-1)) locations. A GIS approach was applied to calculate the contribution of gullies to landscape scale greenhouse gas fluxes. Findings from the Moor House National Nature Reserve in the UK showed that although gullies occupied only 9.3% of the total land surface, gullies accounted for 95.8% and 21.6% of the peatland net CH(4) and CO(2) respiratory fluxes, respectively. The implication of these findings is that the relative contribution of characteristic gully systems need to be considered in estimates of landscape scale peatland greenhouse gas fluxes.     

Soil pollution by oxidation of tailings from toxic spill of a pyrite mine.

On the 25th April 1998, toxic water and tailings from a pyrite mine of Aznalcóllar (southern Spain) spilled into the Agrio and Guadiamar River Basin affecting some 40 km2. In five sectors throughout the basin, we monitored the physical and chemical properties of the tailings as well as the degree of pollution in the soils on four different sampling dates: 5 May, 20 May, 4 June and 22 July 1998. The characteristics of the tailings deposited on the soils are shown to be related to distance from the spill. The oxidation rate of the tailings and the solubilization of the pollutant elements were more pronounced in the middle and lower sectors of the basin, where the particle size was finer, the sulfur content higher and the bulk density less. The increases in water-soluble sulfates, Zn. Cd and Cu were very rapid (the highest values being reached 25 days after the spill) and intense (reaching 45% of the total Cu, 65% of the total Zn and Cd). Meanwhile, the increases in water-soluble As, Bi, Sb, Pb and Tl were far lower (ranging between 0.002% of the total Tl and 2.5% of the total As) and less rapid in the case of As, Bi and Pb (the highest values for these elements being reached 40 days after the spill). These soluble elements infiltrated the soils with the rainwater, swiftly augmenting the soil pollution. Twenty-five days after the spill, when the rainfall ranged between 45 and 63 mm, the first 10-cm of the soils in the middle and lower sectors of the basin exceeded the maximum concentration permitted for agricultural soils in Zn, Cu and Tl. At 40 days after the spill, when the rainfall ranged between 60 and 89 mm, all the soils reached or exceeded the maximum permitted concentrations for As and Tl. Nevertheless, the pollutants tended to concentrate in the first 10 cm of the soils without seriously contaminating either the subsoil or the groundwaters. Consequently, a rapid removal of the tailings and the ploughing of the first 25-30 cm of the soils would be urgent measures to diminish pollutant concentration in the soils affected by the spill.