An examination of groundwater discharge and the associated nutrient fluxes into the estuaries of eastern Hainan Island, China using 226Ra

The nutrient concentrations and stoichiometry in a coastal bay/estuary are strongly influenced by the direct riverine discharge and the submarine groundwater discharge (SGD). To estimate the fluxes of submarine groundwater discharge into the Bamen Bay (BB) and the Wanquan River Estuary (WQ) of eastern Hainan Island, China, the naturally occurring radium isotope (²²⁶Ra) was measured in water samples collected in the bay/estuary in August 2007 and 2008. Based on the distribution of ²²⁶Ra in the surface water, a 3-end-member mixing model was used to estimate the relative contributions of the sources to these systems. Flushing times of 3.9 ± 2.7 and 12.9 ± 9.3 days were estimated for the BB and WQ, respectively, to calculate the radium fluxes for each system. Based on the radium fluxes from groundwater discharge and the Ra isotopic compositions in the groundwater samples, the estimated SGD fluxes were 3.4 ± 5.0 m³ s⁻¹ in the BB and 0.08 ± 0.08 m³ s⁻¹ in the WQ, or 16% and 0.06%, respectively, of the local river discharge. Using this information, the nutrient fluxes from the submarine groundwater discharge seeping into the BB and WQ regions were estimated. In comparison with the nutrient fluxes from the local rivers, the SGD-derived nutrient fluxes played a vital role in controlling the nutrient budgets and stoichiometry in the study area, especially in the BB.     

Effect of organic enrichment and thermal regime on denitrification and dissimilatory nitrate reduction to ammonium (DNRA) in hypolimnetic sediments of two lowland lakes

We analyzed benthic fluxes of inorganic nitrogen, denitrification and dissimilatory nitrate reduction to ammonium (DNRA) rates in hypolimnetic sediments of lowland lakes. Two neighbouring mesotrophic (Ca' Stanga; CS) and hypertrophic (Lago Verde; LV) lakes, which originated from sand and gravel mining, were considered. Lakes are affected by high nitrate loads (0.2-0.7 mM) and different organic loads. Oxygen consumption, dissolved inorganic carbon, methane and nitrogen fluxes, denitrification and DNRA were measured under summer thermal stratification and late winter overturn.Hypolimnetic sediments of CS were a net sink of dissolved inorganic nitrogen (−3.5 to −4.7 mmol m⁻² d⁻¹) in both seasons due to high nitrate consumption. On the contrary, LV sediments turned from being a net sink during winter overturn (−3.5 mmol m⁻² d⁻¹) to a net source of dissolved inorganic nitrogen under summer conditions (8.1 mmol m⁻² d⁻¹), when significant ammonium regeneration was measured at the water-sediment interface. Benthic denitrification (0.7-4.1 mmol m⁻² d⁻¹) accounted for up to 84-97% of total NO₃⁻ reduction and from 2 to 30% of carbon mineralization. It was mainly fuelled by water column nitrate. In CS, denitrification rates were similar in winter and in summer, while in LV summer rates were 4 times lower. DNRA rates were generally low in both lakes (0.07-0.12 mmol m⁻² d⁻¹). An appreciable contribution of DNRA was only detected in the more reducing sediments of LV in summer (15% of total NO₃⁻ reduction), while during the same period only 3% of reduced NO₃⁻ was recycled into ammonium in CS.Under summer stratification benthic denitrification was mainly nitrate-limited due to nitrate depletion in hypolimnetic waters and parallel oxygen depletion, hampering nitrification. Organic enrichment and reducing conditions in the hypolimnetic sediment shifted nitrate reduction towards more pronounced DNRA, which resulted in the inorganic nitrogen recycling and retention within the bottom waters. The prevalence of DNRA could favour the accumulation of mineral nitrogen with detrimental effects on ecosystem processes and water quality.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.     

Environmental impact of mining activities in the Lousal area (Portugal): chemical and diatom characterization of metal-contaminated stream sediments and surface water of Corona stream

Lousal mine is a typical “abandoned mine” with all sorts of problems as consequence of the cessation of the mining activity and lack of infrastructure maintenance. The mine is closed at present, but the heavy metal enriched tailings remain at the surface in oxidizing conditions. Surface water and stream sediments revealed much higher concentrations than the local geochemical background values, which the “Contaminated Sediment Standing Team” classifies as very toxic. High concentrations of Cu, Pb, Zn, As, Cd and Hg occurred within the stream sediments downstream of the tailings sites (up to: 817 mg kg⁻¹ As, 6.7 mg kg⁻¹ Cd, 1568 mg kg⁻¹ Cu, 1059 mg kg⁻¹ Pb, 82.4 mg kg⁻¹ Sb, 4373 mg kg⁻¹ Zn). The AMD waters showed values of pH ranging from 1.9 to 2.9 and concentrations of 9249 to 20,700 mg L⁻¹ SO₄⁻², 959 to 4830 mg L⁻¹ Fe and 136 to 624 mg L⁻¹ Al. Meanwhile, the acid effluents and mixed stream waters also carried high contents of SO₄^2−, Fe, Al, Cu, Pb, Zn, Cd, and As, generally exceeding the Fresh Water Aquatic Life Acute Criteria. Negative impacts in the diatom communities growing at different sites along a strong metal pollution gradient were shown through Canonical Correspondence Analysis: in the sites influenced by Acid Mine Drainage (AMD), the dominant taxon was Achnanthidium minutissimum. However, Pinnularia acoricola was the dominant species when the environmental conditions were extremely adverse: very low pH and high metal concentrations (sites 2 and 3). Teratological forms of Achnanthidium minutissimum (Kützing) Czarnecki, Brachysira vitrea (Grunow) Ross in Hartley, Fragilaria rumpens (Kützing) G. W. F. Carlson and Nitzschia hantzschiana Rabenhorst were found. A morphometric study of B. vitrea showed that a decrease in size was evident at the most contaminated sites. These results are evidence of metal and acidic pollution.     

Seasonality of diffusive exchange of polychlorinated biphenyls and hexachlorobenzene across the air-sea interface of Kaohsiung Harbor, Taiwan

Gaseous and dissolved concentrations of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) were measured in the ambient air and water of Kaohsiung Harbor lagoon, Taiwan, from December 2003 to January 2005. During the rainy season (April to September), gaseous PCB and HCB concentrations were low due to both scavenging by precipitation and dilution by prevailing southwesterly winds blown from the atmosphere of the South China Sea. In contrast, trace precipitation and prevailing northeasterly winds during the dry season (October to March) resulted in higher gaseous PCB and HCB concentrations. Instantaneous air-water exchange fluxes of PCB homologues and HCB were calculated from 22 pairs of air and water samples from Kaohsiung Harbor lagoon. All net fluxes of PCB homologues and HCB in this study are from water to air (net volatilization). The highest net volatile flux observed was + 172 ng m^− 2 day^− 1 (dichlorobiphenyls) in December, 2003 due to the high wind speed and high dissolved concentration. The PCB homologues and HCB fluxes were significantly governed by dissolved concentrations in Kaohsiung Harbor lagoon. For low molecular weight PCBs (LMW PCBs), their fluxes were also significantly correlated with wind speed. The net PCB and HCB fluxes suggest that the annual sums of 69 PCBs and HCB measured in this study were mainly volatile (57.4 × 10³ and 28.3 × 10³ ng m^− 2 yr^− 1, respectively) and estimated yearly, 1.5 kg and 0.76 kg of PCBs and HCB were emitted from the harbor lagoon surface waters to the ambient atmosphere. The average tPCB flux in this study was about one-tenth of tPCB fluxes seen in New York Harbor and in the Delaware River, which are reported to be greatly impacted by PCBs.     

The effects of phytophagous insects on water and soil nutrient concentrations and fluxes through forest stands of the Level II monitoring network in the UK

The effects of insect defoliators on throughfall and soil nutrient fluxes were studied in coniferous and deciduous stands at five UK intensive monitoring plots (1998 to 2008). Links were found between the dissolved organic carbon (DOC), nitrogen (N) and potassium (K) fluxes through the forest system to biological activity within the canopy. Underlying soil type determined the leaching or accumulation of these elements. Under oak, monitored at two sites, frass from caterpillars of Tortrix viridana and Operophtera brumata added direct deposition of ~ 16 kg ha⁻¹extra N during defoliation. Peaks of nitrate (NO₃-N) flux between 5 and 9 kg ha⁻¹ (×5 usual winter values) were recorded in consecutive years in shallow soil waters. Synchronous rises in deep soil NO₃-N fluxes at the Grizedale sandy site indicate downward flushing, not seen at the clay site. Under three Sitka spruce stands, generation of honeydew (DOC) was attributed to two aphid species (Elatobium abietinum and Cinara pilicornis) with distinctive feeding strategies. Throughfall DOC showed mean annual fluxes (6 seasons) ~ 45-60 kg ha⁻¹ compared with rainfall values of 14-22 kg ha⁻¹. Increases of total N in throughfall and NO₃-N fluxes in shallow soil solution were detected — soil water fluxes reached  8 kg ha⁻¹ in Llyn Brianne, ~ 25 kg ha⁻¹ in Tummel, and ~ 40 kg NO₃-N ha⁻¹ in Coalburn. At Tummel, on sandy soil, NO₃-N leaching showed increased concentration at depth, attributed to microbiological activity within the soil. By contrast, at Coalburn and Llyn Brianne, sites on peaty gleys, soil water NO₃-N was retained mostly within the humus layer. Soil type is thus key to predicting N movement and retention patterns. These long term analyses show important direct and indirect effects of phytophagous insects in forest ecosystems, on above and below ground processes affecting tree growth, soil condition, vegetation and water quality.     

Anthropogenic and natural radionuclides in caribou and muskoxen in the western Alaskan Arctic and marine fish in the Aleutian Islands in the first half of 2000s

A number of caribou and muskoxen samples from the western Alaskan Arctic and fish samples from the Aleutian Islands were collected between 1998 and 2006 and analyzed for anthropogenic (⁹⁰Sr and ¹³⁷Cs) and natural radionculides (⁴⁰ K, ²¹⁰Pb and ²²⁶Ra), as part of the radiological assessment for the regional subsistence hunting communities in the first half of 2000s. We examined the relationship between the activities of these nuclides with the size of the fish. In caribou samples, concentration of ⁹⁰Sr in muscle was below the detection limit of 0.14 Bq kg^− 1 and ¹³⁷Cs concentration in bones was below the detection limit of 0.15 Bq kg^− 1.¹³⁷Cs activity varied over an order of magnitude in caribou muscle samples with an average value of 2.5 Bq/kg wet wt. Average ¹³⁷Cs activity in muskoxen muscle was found to be 9.7 Bq/kg wet wt. However, there were a little variation (less than 60%) in ²¹⁰Pb, ⁴⁰ K, and ²²⁶Ra in both muscle and bone of both caribou and muskoxen. The activities of total ²¹⁰Pb in caribou and muskox bones were found to be 1-2 orders of magnitude higher than that of parent-supported ²¹⁰Pb indicating the potential for dating of bones of terrestrial mammals (time elapsed since the death of the animal) based on the excess ²¹⁰Pb method exists. In fish muscle samples, ¹³⁷Cs activity varied from below detection limit to 154 mBq/kg wet wt. and its content increased with the size of the fish due to its transfer through the food chain. Among the seven fish species investigated, ²¹⁰Pb activities varied almost an order of magnitude; however, ⁴⁰K and ²²⁶Ra activities varied less than a factor of two. Total annual effective dose due to ⁹⁰Sr and ¹³⁷Cs from the ingestion of those terrestrial and marine meats was estimated to be negligible (ca. 9 μSV/a) compared to the natural radionuclides present thus posing negligible radiological threat to humans.     

Elemental and organic carbon in aerosols over urbanized coastal region (southern Baltic Sea, Gdynia)

Studies on PM 10, total particulate matter (TSP), elemental carbon (EC) and organic carbon (OC) concentrations were carried out in the Polish coastal zone of the Baltic Sea, in urbanized Gdynia. The interaction between the land, the air and the sea was clearly observed. The highest concentrations of PM 10, TSP and both carbon fractions were noted in the air masses moving from southern and western Poland and Europe. The EC was generally of primary origin and its contribution to TSP and PM 10 mass was on average 2.3% and 3.7% respectively. Under low wind speed conditions local sources (traffic and industry) influenced increases in elemental carbon and PM 10 concentrations in Gdynia. Elemental carbon demonstrated a pronounced weekly cycle, yielding minimum values at the weekend and maximum values on Thursdays. The role of harbors and ship yards in creating high EC concentrations was clearly observed. Concentration of organic carbon was ten times higher than that of elemental carbon, and the average OC contribution to PM 10 mass was very high (31.6%). An inverse situation was observed when air masses were transported from over the Atlantic Ocean, the North Sea and the Baltic Sea. These clean air masses were characterized by the lowest concentrations of all analysed compounds.Obtained results for organic and elemental carbon fluxes showed that atmospheric aerosols can be treated, along with water run-off, as a carbon source for the coastal waters of the Baltic Sea. The enrichment of surface water was more effective in the case of organic carbon (0.27 ± 0.19 mmol m⁻² d⁻¹). Elemental carbon fluxes were one order of magnitude smaller, on average 0.03 ± 0.04 mmol m⁻² d⁻¹. We suggest that in some situations atmospheric carbon input can explain up to 18% of total carbon fluxes into the Baltic coastal waters.     

Summer fluxes of atmospheric greenhouse gases N2O, CH4 and CO2 from mangrove soil in South China

The atmospheric fluxes of N₂O, CH₄ and CO₂ from the soil in four mangrove swamps in Shenzhen and Hong Kong, South China were investigated in the summer of 2008. The fluxes ranged from 0.14 to 23.83 μmol m⁻² h⁻¹, 11.9 to 5168.6 μmol m⁻² h⁻¹ and 0.69 to 20.56 mmol m⁻² h⁻¹ for N₂O, CH₄ and CO₂, respectively. Futian mangrove swamp in Shenzhen had the highest greenhouse gas fluxes, followed by Mai Po mangrove in Hong Kong. Sha Kong Tsuen and Yung Shue O mangroves in Hong Kong had similar, low fluxes. The differences in both N₂O and CH₄ fluxes among different tidal positions, the landward, seaward and bare mudflat, in each swamp were insignificant. The N₂O and CO₂ fluxes were positively correlated with the soil organic carbon, total nitrogen, total phosphate, total iron and NH₄⁺-N contents, as well as the soil porosity. However, only soil NH₄⁺-N concentration had significant effects on CH₄ fluxes.     

Multiple site study of recent atmospheric metal (Pb, Zn and Cu) deposition in the NW Iberian Peninsula using peat cores

In order to estimate atmospheric metal deposition in Southern Europe since the beginning of the Industrial Period (~ 1850 AD), concentration profiles of Pb, Zn and Cu were determined in four ²¹⁰Pb-dated peat cores from ombrotrophic bogs in Serra do Xistral (Galicia, NW Iberian Peninsula). Maximum metal concentrations varied by a factor of 1.8 for Pb and Zn (70 to 128 μg g⁻¹ and 128 to 231 μg g⁻¹, respectively) and 3.5 for Cu (11 to 37 μg g⁻¹). The cumulative metal inventories of each core varied by a factor of 3 for all analysed metals (132 to 329 μg cm⁻² for Pb, 198 to 625 μg cm⁻² for Zn and 22 to 69 μg cm⁻² for Cu), suggesting differences in net accumulation rates among peatlands. Although results suggest that mean deposition rates vary within the studied area, the enhanced ²¹⁰Pb accumulation and the interpretation of the inventory ratios (²¹⁰Pb/Pb, Zn/Pb and Cu/Pb) in two bogs indicated that either a record perturbation or post-depositional redistribution effects must be considered. After correction, Pb, Zn and Cu profiles showed increasing concentrations and atmospheric fluxes since the mid-XX^th century to maximum values in the second half of the XX^th century. For Pb, maximum fluxes were observed in 1955-1962 and ranged from 16 to 22 mg m⁻² yr⁻¹ (mean of 18 ± 1 mg m⁻² yr⁻¹), two orders of magnitude higher than in the pre-industrial period. Peaks in Pb fluxes in Serra do Xistral before the period of maximum consumption of leaded petrol in Europe (1970s-1980s) suggest the dominance of local pollutant sources in the area (i.e. coal mining and burning). More recent peaks were observed for Zn and Cu, with fluxes ranging from 32 to 52 mg m⁻² yr⁻¹ in 1989-1996, and from 4 to 9 mg m⁻² yr⁻¹ in 1994-2001, respectively. Our results underline the importance of multi-core studies to assess both the integrity and reliability of peat records, and the degree of homogeneity in bog accumulation. We show the usefulness of using the excess ²¹⁰Pb inventory to distinguish between differential metal deposition, accumulation or anomalous peat records.     

Effects of wood ash fertilization on forest floor greenhouse gas emissions and tree growth in nutrient poor drained peatland forests

Wood ash (3.1, 3.3 or 6.6 tonnes dry weight ha^− 1) was used to fertilize two drained and forested peatland sites in southern Sweden. The sites were chosen to represent the Swedish peatlands that are most suitable for ash fertilization, with respect to stand growth response. The fluxes of carbon dioxide (CO₂), methane (CH₄) and nitrous oxide (N₂O) from the forest floor, measured using opaque static chambers, were monitored at both sites during 2004 and 2005 and at one of the sites during the period 1 October 2007-1 October 2008. No significant (p > 0.05) changes in forest floor greenhouse gas exchange were detected. The annual emissions of CO₂ from the sites varied between 6.4 and 15.4 tonnes ha^− 1, while the CH₄ fluxes varied between 1.9 and 12.5 kg ha^− 1. The emissions of N₂O were negligible. Ash fertilization increased soil pH at a depth of 0-0.05 m by up to 0.9 units (p < 0.01) at one site, 5 years after application, and by 0.4 units (p < 0.05) at the other site, 4 years after application. Over the first 5 years after fertilization, the mean annual tree stand basal area increment was significantly larger (p < 0.05) at the highest ash dose plots compared with control plots (0.64 m² ha^− 1 year^− 1 and 0.52 m² ha^− 1 year^− 1, respectively). The stand biomass, which was calculated using tree biomass functions, was not significantly affected by the ash treatment. The groundwater levels during the 2008 growing season were lower in the high ash dose plots than in the corresponding control plots (p < 0.05), indicating increased evapotranspiration as a result of increased tree growth. The larger basal area increment and the lowered groundwater levels in the high ash dose plots suggest that fertilization promoted tree growth, while not affecting greenhouse gas emissions.     

Particle deposition fluxes of BDE-209, PAHs, DDTs and chlordane in the Pearl River Delta, South China

Year-round bulk air deposition samples were collected at 15 sites in the Pearl River Delta (PRD) on a bimonthly basis from Dec 2003 to Nov 2004, and the particle-phase deposition of BDE-209, PAHs, DDTs and chlordane was measured. The annual deposition fluxes of BDE-209, total PAHs (15 compounds), total DDT (sum of p,p′-DDE, p,p′-DDD, p,p′-DDT, and o,p′-DDT ), and chlordane (sum of trans-chlordane and cis-chlordane) varied from 32.6 to 1970 μg m^− 2 yr^− 1, 22 to 290 μg m^− 2 yr^− 1, 0.8 to 11 μg m^− 2 yr^− 1, and 0.25 to 1.9 μg m^− 2 yr^− 1, respectively. Spatial variations were higher in the centre of the PRD and lower at the coastal sites for all compounds. The seasonal variations of deposition were found to be compound-dependent, influenced by a number of factors, such as the timing of source input, temperature, and precipitation etc. In particular, source input time affected the deposition fluxes of BDE-209 and high-weight PAHs, while temperature-dependent gas-particle partitioning was a key factor for DDT and light-weight PAH deposition. During the whole sampling period, the atmospheric deposition of BDE-209, ΣPAHs, ΣDDTs, and chlordane onto Hong Kong reached about 93, 86, 2.1 and 2.1 kg yr^− 1, respectively, and onto the PRD reached about 13,400, 2950, 82, and 63 kg yr^− 1. By comparing the calculated total air deposition with the burden in the soils, the half residual time of BDE-209 in soils was estimated to be 3 years.     

Organic and inorganic carbon concentrations and fluxes from managed and unmanaged boreal first-order catchments

Seasonal and between stream variation (catchment dependent variation) in losses of organic and inorganic carbon via downstream transport and outgassing of CO₂ into the atmosphere were studied in 11 small boreal catchments situated in close proximity to each other. Of these catchments four were undrained peatland rich catchments, four drained peatland rich catchments and three managed mineral soil-dominated catchments. Downstream export of total inorganic carbon (TIC) varied between 870 and 1400 kg km^− 2 a^− 1 and was rather consistent between the catchments, except in the case of the mineral soil-dominated catchment Kangaslampi, where export was only 420 kg km^− 2 a^− 1. The export of total organic carbon (TOC) varied between 2300 and 14,800 kg km^− 2 a^− 1 and was highest in peatland rich catchments. Peatland drainage decreased TIC and TOC concentrations in the long term, but did not affect lateral carbon export due to increased runoff from the catchments. Partial pressure of CO₂ in streams was the highest in undrained peatland rich catchments, but the outgassing of CO₂ into the atmosphere was also high from drained peatlands due to the higher discharge rate and long ditch networks. In mineral soil-dominated catchments both downstream export of carbon and emission into the atmosphere were low. TOC exports were compared in two climatically different years (2003 and 2007). The results indicate that climate change might alter the timing of the TOC export from the catchments, the importance of the spring ice melt diminishing and both snow cover and snow free period export increasing.     

Occurrence of arsenic in core sediments and groundwater in the Chapai-Nawabganj District, northwestern Bangladesh

Groundwater and core sediments of two boreholes (to a depth of 50 m) from the Chapai-Nawabganj area in northwestern Bangladesh were collected for arsenic concentration and geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10-40 m of depth) range from 2.8 μg L⁻¹ to 462.3 μg L⁻¹. Groundwater geochemical conditions change from oxidized to successively more reduced, higher As concentration with depth. Higher sediment arsenic levels (55 mg kg⁻¹) were found within the upper 40 m of the drilled core samples. X-ray absorption near-edge structure spectroscopy was employed to elucidate the arsenic speciation of sediments collected from two boreholes. Environmental scanning electron microscopy and transmission X-ray microscopy were used to investigate the characteristics of FeOOH in sediments which adsorb arsenic. In addition, a pH-Eh diagram was drawn using the Geochemist's Workbench (GWB) software to elucidate the arsenic speciation in groundwater. The dominant groundwater type is Ca-HCO₃ with high concentrations of As, Fe and Mn but low levels of NO₃⁻ and SO₄²⁻. Sequential extraction analysis reveals that Mn and Fe hydroxides and organic matter are the major leachable solids carrying As. High levels of arsenic concentration in aquifers are associated with fine-grained sediments. Fluorescent intensities of humic substances indicate that both groundwater and sediments in this arsenic hotspot area contain less organic matter compared to other parts of Bengal basin. Statistical analysis clearly shows that As is closely associated with Fe and Mn in sediments while As is better correlated with Mn in groundwater. These correlations along with results of sequential leaching experiments suggest that reductive dissolution of MnOOH and FeOOH mediated by anaerobic bacteria represents an important mechanism for releasing arsenic into the groundwater.     

Migration behavior of landfill leachate contaminants through alternative composite liners

Four identical pilot-scale landfill reactors with different alternative composite liners were simultaneously operated for a period of about 540 days to investigate and to simulate the migration behaviors of phenolic compounds (phenol, 2-CP, 2-MP, 3-MP, 4-MP, 2-NP, 4-NP, 2,4-DNP, 2,4-DCP, 2,6-DCP, 2,4,5-TCP, 2,4,6-TCP, 2,3,4,6-TeCP, PCP) and heavy metals (Pb, Cu, Zn, Cr, Cd, Ni) from landfill leachate to the groundwater. Alternative landfill liners of four reactors consist of R1: Compacted clay liner (10 cm + 10 cm, k = 10⁻⁸ m/sn), R2: Geomembrane (2 mm HDPE) + compacted clay liner (10 cm + 10 cm, k = 10⁻⁸ m/sn), R3: Geomembrane (2 mm HDPE) + compacted clay liner (10 cm, k = 10⁻⁸ m/sn) + bentonite liner (2 cm) + compacted clay liner (10 cm, k = 10⁻⁸ m/sn), and R4: Geomembrane (2 mm HDPE) + compacted clay liner (10 cm, k = 10⁻⁸ m/sn) + zeolite liner (2 cm) + compacted clay liner (10 cm, k = 10⁻⁸ m/sn). Wastes representing Istanbul municipal solid wastes were disposed in the reactors. To represent bioreactor landfills, reactors were operated by leachate recirculation. To monitor and control anaerobic degradation in the reactors, variations of conventional parameters (pH, alkalinity, chloride, conductivity, COD, TOC, TKN, ammonia and alcaly metals) were also investigated in landfill leachate samples. The results of this study showed that about 35-50% of migration of organic contaminants (phenolic compounds) and 55-100% of migration of inorganic contaminants (heavy metals) to the model groundwater could be effectively reduced with the use of bentonite and zeolite materials in landfill liner systems. Although leachate contaminants can reach to the groundwater in trace concentrations, findings of this study concluded that the release of these compounds from landfill leachate to the groundwater may potentially be of an important environmental concern based on the experimental findings.     

Contribution from the primary and secondary sources to the atmospheric formaldehyde in Kolkata, India

A novel and straight forward method is adopted to segregate the contribution of primary and secondary sources of formaldehyde based on the rates of its formation and removal at different times in the urban atmosphere of Kolkata. To achieve the above objective, the diurnal and seasonal mixing ratios of formaldehyde were measured during dry season at two busy roadside locations. The maximal secondary formation fluxes of formaldehyde during summer and winter were found to be 6.63 × 10⁷ and 1.23 × 10⁷ molecules cm^− 3 s^− 1, respectively. Apart from formaldehyde (C₁), several other carbonyls were quantified in this study. An overall good correlation between acetaldehyde (C₂) and propanal (C₃) indicates the contribution of vehicular emission to the carbonyl budget. The secondary formaldehyde contributions in summer and winter were about 71% and 32%, respectively. The relative mean contributions of C₁, C₂ and ozone towards generation of OH fluxes in summer were found to be 1.56 × 10⁷, 6.96 × 10⁵, and 1.29 × 10⁷ molecules cm^− 3 s^− 1, respectively, which were 3.2, 3.4 and 1.6 times higher than those in winter.     

Manganese concentrations in Scottish groundwater

Groundwater is increasingly being used for public and private water supplies in Scotland, but there is growing evidence that manganese (Mn) concentrations in many groundwater supplies exceed the national drinking water limit of 0.05 mg l^− 1. This study examines the extent and magnitude of high Mn concentrations in groundwater in Scotland and investigates the factors controlling Mn concentrations. A dataset containing 475 high quality groundwater samples was compiled using new data from Baseline Scotland supplemented with additional high quality data where available. Concentrations ranged up to 1.9 mg l^− 1; median Mn concentration was 0.013 mg l^− 1 with 25th and 75th percentiles 0.0014 and 0.072 mg l^− 1 respectively. The Scottish drinking water limit (0.05 mg l^− 1) was exceeded for 30% of samples and the WHO health guideline (0.4 mg l^− 1) by 9%; concentrations were highest in the Carboniferous sedimentary aquifer in central Scotland, the Devonian sedimentary aquifer of Morayshire, and superficial aquifers. Further analysis using 137 samples from the Devonian aquifers indicated strong redox and pH controls (pH, Eh and dissolved oxygen accounted for 58% of variance in Mn concentrations). In addition, an independent relationship between Fe and Mn was observed, suggesting that Fe behaviour in groundwater may affect Mn solubility. Given the redox status and pH of Scottish groundwaters the most likely explanation is sorption of Mn to Fe oxides, which are released into solution when Fe is reduced.Since the occurrence of elevated Mn concentrations is widespread in groundwaters from all aquifer types, consideration should be given to monitoring Mn more widely in both public and private groundwater supplies in Scotland and by implication elsewhere.     

Gross CO2 and CH4 emissions from the Nam Ngum and Nam Leuk sub-tropical reservoirs in Lao PDR

Gross CO₂ and CH₄ emissions (degassing and diffusion from the reservoir) and the carbon balance were assessed in 2009-2010 in two Southeast Asian sub-tropical reservoirs: the Nam Ngum and Nam Leuk Reservoirs (Lao PDR). These two reservoirs are within the same climatic area but differ mainly in age, size, residence time and initial biomass stock. The Nam Leuk Reservoir was impounded in 1999 after partial vegetation clearance and burning. However, GHG emissions are still significant 10 years after impoundment. CH₄ diffusive flux ranged from 0.8 (January 2010) to 11.9 mmol m^− 2 d^− 1 (April 2009) and CO₂ diffusive flux ranged from - 10.6 (October 2009) to 38.2 mmol m^− 2 d^− 1 (April 2009). These values are comparable to other tropical reservoirs. Moreover, degassing fluxes at the outlet of the powerhouse downstream of the turbines were very low. The tentative annual carbon balance calculation indicates that this reservoir was a carbon source with an annual carbon export (atmosphere + downstream river) of about 2.2 ± 1.0 GgC yr^− 1.The Nam Ngum Reservoir was impounded in 1971 without any significant biomass removal. Diffusive and degassing CO₂ and CH₄ fluxes were lower than for other tropical reservoirs. Particularly, CO₂ diffusive fluxes were always negative with values ranging from - 21.2 (April 2009) to - 2.7 mmol m⁻² d⁻¹ (January 2010). CH₄ diffusive flux ranged from 0.1 (October 2009) to 0.6 mmol m⁻² d⁻¹ (April 2009) and no degassing downstream of the turbines was measured. As a consequence of these low values, the reservoir was a carbon sink with an estimated annual uptake of - 53 ± 35 GgC yr⁻¹.     

Impact of selected agricultural management options on the reduction of nitrogen loads in three representative meso scale catchments in Central Germany

Nitrogen inputs into surface waters from diffuse sources are still unduly high and the assessment of mitigation measures is associated with large uncertainties. The objective of this paper is to investigate selected agricultural management scenarios on nitrogen loads and to assess the impact of differing catchment characteristics in central Germany. A new modelling approach, which simulates spatially distributed N-transport and transformation processes in soil and groundwater, was applied to three meso scale catchments with strongly deviating climate, soil and topography conditions. The approach uses the integrated modelling framework JAMS to link an agro-ecosystem, a rainfall-runoff and a groundwater nitrogen transport model. Different agricultural management measures with deviating levels of acceptance were analysed in the three study catchments.N-leaching rates in all three catchments varied with soil type, the lowest leaching rates being obtained for loess soil catchment (18.5 kg nitrate N ha^− 1 yr^− 1) and the highest for the sandy soils catchment (41.2 kg nitrate N ha^− 1 yr^− 1). The simulated baseflow nitrogen concentrations varied between the catchments from 1 to 6 mg N l^− 1, reflecting the nitrogen reduction capacity of the subsurfaces. The management scenarios showed that the highest N leaching reduction could be achieved by good site-adapted agricultural management options. Nitrogen retention in the subsurface did not alter the ranking of the management scenarios calculated as losses from the soil zone. The reduction effect depended strongly on site specific conditions, especially climate, soil variety and the regional formation of the crop rotations.     

Kinetics of nitrate and perchlorate reduction in ion-exchange brine using the membrane biofilm reactor (MBfR)

Several sources of bacterial inocula were tested for their ability to reduce nitrate and perchlorate in synthetic ion-exchange spent brine (30-45 g/L) using a hydrogen-based membrane biofilm reactor (MBfR). Nitrate and perchlorate removal fluxes reached as high as 5.4 g N m⁻² d⁻¹ and 5.0 g ClO₄ m⁻² d⁻¹, respectively, and these values are similar to values obtained with freshwater MBfRs. Nitrate and perchlorate removal fluxes decreased with increasing salinity. The nitrate fluxes were roughly first order in H₂ pressure, but roughly zero-order with nitrate concentration. Perchlorate reduction rates were higher with lower nitrate loadings, compared to high nitrate loadings; this is a sign of competition for H₂. Nitrate and perchlorate reduction rates depended strongly on the inoculum. An inoculum that was well acclimated (years) to nitrate and perchlorate gave markedly faster removal kinetics than cultures that were acclimated for only a few months. These results underscore that the most successful MBfR bioreduction of nitrate and perchlorate in ion-exchange brine demands a well-acclimated inoculum and sufficient hydrogen availability.