Phosphate adsorption by riverborne clay sediments in a southern-Italy Mediterranean reservoir: Insights from a "natural geo-engineering" experiment.

This paper reports data from a southern-Italy reservoir (Lake Occhito) characterized by a strong riverborne sediment transport. Main hydrochemical, trophic, and nutrient variables were measured (over a twelve-month period) in both lake and tributaries. Lacustrine sediments were subjected to mineralogical characterization and to phosphorus fractioning, while a 6-day long batch experiment was carried out to evaluate the lake sediment orthophosphate adsorption capacity. A set of algal growth potential tests was also undertaken on the lake and its tributaries. Results highlight the presence of a strong gradient in nutrient availability among the inflows. Most of the nutrient loads were from the main tributary (20.3 t P a-1, ~83 %), that showed the highest trophic potential (average: 56.8 mg L-1) and was nitrogen/phosphorus co-limited. The other inflows were phosphorus limited and characterized by a higher sediment transport. The lake showed the lowest nutrient concentrations (average total phosphorus: 21 µg P L-1) and was strongly phosphorus limited. Clays were the principal minerals in the lake sediments (~51 %), while the main phosphorus fraction was apatite (~78 %). The batch experiment demonstrated the capability of the lake sediments to reduce orthophosphate concentrations in phosphorus-rich waters (initial orthophosphate: 320 µg P L-1; ~80 % reduction). The lake sediment orthophosphate kinetics of abatement was similar to that of a commercially available phosphorus sorbent (lanthanum modified bentonite), although the stability of phosphorus binding was higher for the commercial product. Theoretical average in-lake total phosphorus, chlorophyll-a, and transparency values, estimated through Vollenweider models, were approximately double of the average values measured in the lake. Therefore, the massive presence of riverborne clay sediments seems to markedly reduce the in-lake orthophosphate concentrations (and light penetration), inducing an overall lowering of the lake trophic state, as if the lake ecosystem were permanently subjected to a geo-engineering phosphorus sorbent treatment.

Manganese-mediated hydrochemistry and microbiology in a meromictic subalpine lake (Lake Idro, Northern Italy) - A biogeochemical approach.

This study presents the findings from several field campaigns carried out in Lake Idro (Northern Italy), a deep (124 m) meromictic-subalpine lake, whose water column is subdivided in a mixolimnion (~0-40 m) and a monimolimnion (~40-124 m). Hydrochemical data highlight two main peculiarities characterizing the Lake Idro meromixis: a) presence of a high manganese/iron ratio (up to 20 mol/mol), b) absence of a clear chemocline between the two main layers. The high manganese content contributed to the formation of a stable manganese dominated deep turbid stratum (40-65 m), enveloping the redoxcline (~45-55 m) in the upper monimolimnion. The presence of this turbid stratum in Lake Idro is described for the first time in this study. The paper examines the distribution of dissolved and particulate forms of transition metals (Mn and Fe), alkaline earth metals (Ca and Mg), and other macro-constituents or nutrients (S, P, NO3-N, NH4-N), discussing their behavior over the redoxcline, where the main transition processes occur. Field measurements and theoretical considerations suggest that the deep turbid stratum is formed by a complex mixture of manganese and iron compounds with a prevalence of Mn(II)/Mn(III) in different forms including dissolved, colloidal, and fine particles, that give to the turbid stratum a white-pink opalescent coloration. The bacteria populations show a clear stratification with the upper aerobic layer dominated by the heterotrophic Flavobacterium sp., the turbid stratum hosting a specific microbiological pool, dominated by Caldimonas sp., and the deeper anaerobic layer dominated by the sulfur-oxidizing and denitrifier Sulfuricurvum sp. The occurrence in August 2010 of an anomalous lake surface coloration lasting about four weeks and developing from milky white-green to red-brown suggests that the upper zone of the turbid stratum could be eroded during intense weather-hydrological conditions with the final red-brown coloration resulting from the oxidation of Mn(II)/Mn(III) to Mn(IV) compounds.

Phosphorus content in a deep river sediment core as a tracer of long-term (1962-2011) anthropogenic impacts: A lesson from the Milan metropolitan area.

Reconstructions of past fluvial contamination through the analysis of deep sediment cores are rarely reported in literature. We examined the phosphorus fractions in a deep (2.6 m) sediment core of the Lambro River downstream of the highly anthropized Milan metropolitan area and upstream of the Po river the main Italian watercourse. The core covered the period 1962-2011. Total phosphorus concentrations resulted typical of a strongly impacted environment (4788 mg P kg DW-1 on average) with the highest concentrations related to the 1960s (7639 mg P kg DW-1) reflecting the period of maximum demographic growth. Afterwards, phosphorus concentrations decreased thanks to the infrastructural and legislative initiatives carried out in the 1980s and the 1990s to reduce the impact of urban point sources. Subsequently, total phosphorus concentrations stabilized on values around 3000 mg P kg DW-1 and did not diminish further, even after the second phase of infrastructural interventions carried out in the second half of the 2000s. This was related to the increasing relative impact of the combined sewer overflows in the sewage system and to the strong phosphorus enrichment of the basin. Most of the phosphorus was in inorganic forms (86% of the total) that have been identified as the final target of the domestic effluent inputs. The contribution of organic phosphorus was lower but constant over the period 1962-2011. It likely originated from the agricultural areas located south of the city of Milan. In conclusion, this study underlines how past interventions have been effective in reducing urban point sources but it also highlights the current difficulties related to the growing importance of other sources influenced by the surface runoff (i.e., combined sewer overflows and agriculture). The study also emphasizes a general phosphorus enrichment of the Lambro River basin and its impact on the Po River and the Adriatic Sea.

Chemical characterization of biomass fuel particulate deposits and ashes in households of Mt. Everest region (NEPAL).

During a sampling campaign, carried out during June 2012, inside some traditional households located in four villages (Phakding, Namche, Pangboche and Tukla) of Mt. Everest region in southern part of the central Himalaya (Nepal), particulate matter (PM) depositions and ashes have been collected. Moreover, outdoor PM depositions have also been analyzed. Chemical characterization of PM depositions and ashes for major ions, organic carbon, elemental carbon (EC), metal content and PAHs (Polycyclic Aromatic Hydrocarbons) allowed identifying, as major contributes to indoor PM, the following sources: biomass burning, cooking and chimney ashes. These sources significantly affect outdoor PM depositions: in-house biomass burning is the major source for outdoor EC and K+ as well as biomass burning and cooking activities are the major sources for Polycyclic Aromatic Hydrocarbons.

Glacier Melting Increases the Solute Concentrations of Himalayan Glacial Lakes.

Over the past two decades, we observed a substantial rise in ionic content that was mainly determined by the sulfate concentration at 20 remote high elevation lakes located in central southern Himalaya. At LCN9, which was monitored on an annual basis for the last 20 years, the sulfate concentrations increased over 4-fold. Among the main causes, we exclude a change in the composition of wet atmospheric deposition, as well as a possible influence of decrease in seasonal snow cover duration, which could have exposed larger basin surfaces to alteration processes. Glacier retreat likely was the main factor responsible for the observed increase of sulfate concentrations. We attribute this chemical changes mainly to the sulfide oxidation processes that occur in subglacial environments. Moreover, we observe that the weakened monsoon of the past two decades has only partially contributed to the lakes enrichment through runoff waters that are more concentrated in solutes or lowering the water table, resulting in more rock exposed to air and enhanced mineral oxidation.

Eutrophication management in surface waters using lanthanum modified bentonite: A review.

This paper reviews the scientific knowledge on the use of a lanthanum modified bentonite (LMB) to manage eutrophication in surface water. The LMB has been applied in around 200 environments worldwide and it has undergone extensive testing at laboratory, mesocosm, and whole lake scales. The available data underline a high efficiency for phosphorus binding. This efficiency can be limited by the presence of humic substances and competing oxyanions. Lanthanum concentrations detected during a LMB application are generally below acute toxicological threshold of different organisms, except in low alkalinity waters. To date there are no indications for long-term negative effects on LMB treated ecosystems, but issues related to La accumulation, increase of suspended solids and drastic resources depletion still need to be explored, in particular for sediment dwelling organisms. Application of LMB in saline waters need a careful risk evaluation due to potential lanthanum release.

Surrogate measures for providing high frequency estimates of total phosphorus concentrations in urban watersheds.

Until robust in situ sensors for total phosphorus (TP) are developed, continuous water quality measurements have the potential to be used as surrogates for generating high frequency estimates. Their use has widespread implications for water quality monitoring programmes considering that TP, in particular, is generally recognised as the limiting factor in the process of eutrophication. Surrogate measures for TP concentration, such as turbidity, have proved useful within natural and agricultural contexts, but their predictive capability for urban watersheds is considered more difficult, due to the different sources of TP, though a strict relationship with turbidity/suspended matter has been clearly described even for these environments. In this context, we investigated this still unresolved problem for high frequency estimation of TP concentration in urban environments by monitoring a medium-sized (71 km(2)) urban watershed (Lambro River watershed, north Italy) in which we detected 60 active combined sewer overflows, and an its natural sub-basin for comparison. We found two different relationships between turbidity and TP concentration in the investigated urban watershed that differently describe the prevalence of TP from point sources (domestic wastewaters) or diffuse origin (surface runoff). In this regard, we first characterise the prevailing sources of TP by using a marker for detecting domestic wastewater contamination (caffeine), then we describe the mutual relationships amongst the continuously monitored variables (in our case the occurrence of the First Flush and the clockwise turbidity/discharge hysteresis). Afterwards we discriminate, by observing variables that are continuously monitored (in our case, the discharge and the turbidity), amongst the continuous surrogate records according to their sources. In conclusion, we are able to apply the relevant turbidity/TP regression equations to each turbidity record and, thus, estimate the respective TP concentrations with high frequency. If traditional grab sampling techniques had been employed, the contributions of point sources (up to 34% across 237 monitored days) to the total estimated loads would not have been correctly evaluated, whilst the high frequency monitoring is able to catch the dynamics that occur over time scales of a few hours. We conclude that the reasonable uncertainty obtained in this study can be achieved in other urban watersheds, but further studies are required for watersheds of differing sizes and degrees of urbanisation.

Total phosphorus reference condition for subalpine lakes: a comparison among traditional methods and a new process-based watershed approach.

Different methods for estimating the total phosphorus (TP) reference conditions of lakes have rarely been compared. This work tests the uncertainty and accuracy of the most frequently used approaches (Morpho-edaphic index -MEI-, export coefficient, diatoms and pigment-inferred TP models) for 35 subalpine lakes. Furthermore, we propose a new process-based watershed approach that was tested on a subalpine environment and consists of combining a space for time substitution with a space for space substitution. The possible presence of uncontaminated or less contaminated environments inside or next to the watershed can be exploited by training a hydrological transport watershed model according to the uncontaminated conditions and then applying the calibration to the entire watershed, which reconstructs a natural or semi-natural TP load scenario. We found that the root mean square error (RMSE) for the MEI is 4 µg L(-1). However, its application is limited for lakes that present with an alkalinity ≤1 meq L(-1). For lakes with a higher alkalinity, we observed a loss of predictive capability that results from the lower solubility of phosphorus under conditions of high calcium content. The export coefficient model was applied with a mean export coefficient and presents similar prediction capabilities as the MEI. The chlorophyll-inferred TP model shows a higher uncertainty (RMSE = 8 µg L(-1)); however, it produced fewer underestimations and overestimations. With regards to the diatom-inferred TP model, we are only able to evaluate an uncertainty of 5 µg L(-1) at the European level. Finally, the proposed process-based watershed approach adequately predicted the reference condition of the selected lake and had an uncertainty lower than the other methods (2 µg L(-1)). We conclude by revealing the potential and limitations of this approach in the field of ecological lake modelling more and more attracted by TP pristine load inputs in studies on the effects of climate change and eutrophication of lakes.

Multiple Carrying Capacities from a management-oriented perspective to operationalize sustainable tourism in protected areas.

This article describes how the concept of Tourism Carrying Capacity (TCC) has shifted from a uni-dimensional approach to incorporating environmental, social and political aspects. This shift is demonstrated by a study of a large, internationally popular protected area used by trekkers, the Mt. Everest Region, where qualitative data collected from visitors was combined with environmental modeling using a participatory framework. Tourist satisfaction showed positive margins for further tourist industry expansion, but current environmental conditions limit growth and further development. Space and time dimensions were also considered. We observed that the limits on growth and further development can be manipulated, with a certain degree of flexibility, through investments and regulatory measures. We hypothesized that TCC can play an important role in the management of protected areas only if it is viewed as a systematic, strategic policy tool within a planning process rather than as a unique, intrinsic number that is not modifiable. We conclude that to translate the strategy into action using standard measures, further investigation is needed to balance the various TCC components as a part of a decision-making framework that includes the integration of different cultural approaches and policy needs.

Quality assessment of bed sediments of the Po River (Italy).

Comprehensive and contemporary evaluations of physical, chemical and toxicological endpoints have been performed on bed sediments of the Po River, the major Italian watercourse. Two extensive sampling campaigns were conducted in summer and winter low-flow conditions. Composite sediment samples were collected from ten reaches of the main river: the first was located in the upper region (ambient control), and the others downstream of the confluences of nine principal tributaries. The two sampling programs were paralleled by contemporary investigations on the macroinvertebrate community. The particle-size composition along the Po River showed a relatively uniform distribution of fine sand, a progressive downstream decrease of coarse sands and a corresponding increase of fine materials. The levels of polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), extractable organo halides (EOX), Cd, Cr, Cu, Hg, Ni, Pb and Zn were determined in sediment fine particles (< 63 microm), and showed marked changes across the ten river reaches. Their longitudinal trends, as those of organic carbon and total nitrogen, were very similar and largely independent of the survey season. Sediment quality benchmarks were used to evaluate sediment chemistry, and, although the overall level of contamination was from moderate to low, the reaches located downstream of the tributaries Dora Riparia, Dora Baltea, Lambro and Oglio were considered to be at risk. Sediments were tested for toxicity on Oncorhynchus mykiss, Ceriodaphnia dubia, Raphidocelis subcapitata and Vibrio fischeri. The toxicity tests were conducted both with sediment extracts and whole samples. Sediment extracts showed toxic potentials that were consistent with the spatial distribution of contaminants. Whole-sediment toxicity showed moderate/low effects which also included false positives and negatives. Alterations of the macroinvertebrate community were found for many kilometers downstream of Dora Riparia, and with a seasonal dependence, also in other reaches of the Italian river. Principal component analysis (PCA) was used to describe the longitudinal and temporal changes of the Po River, and allowed the selection of the most useful and discriminating indicators.