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.

A bibliometric review on the Water Framework Directive twenty years after its birth.

The European Water Framework Directive (WFD) is one of the most studied environmental legislations and recently turned twenty. The paper deals with a literature search and analysis of 4120 references related to this Directive. After a period of strong increase in article production (2002-2012) WFD scientific productivity is currently still high (~ 260 papers year-1), suggesting a persistent interest of the scientific community on this issue. Most research supporting the WFD was on water sciences, but contributions were also from governance and socio-economic disciplines. Studies on biological quality elements and rivers were prominent. The WFD implementation has seen a strong participation of scientists from all EU countries, and partially also from outside-EU nations. To improve the EU water policy and management, the paper suggests a greater interconnection between WFD and other EU Directives and indicates some emerging environmental issues to which the Directive should address.

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.

Generation and dispersion of chemical and biological gradients in a large-deep multi-basin lake (Lake Como, north Italy): The joint effect of external drivers and internal wave motions.

The formation of chemical and biological heterogeneity in lakes can be favored by physical and morphometric constrains. This study describes the results of four whole-lake field campaigns carried out in Lake Como (north Italy) during thermal stratification. The aim was to analyze the distribution of chemical-biological variables in a multi-basin lake as a result of internal and external physical drivers and constrains. Lake Como has a y-like shape encompassing three main sub-basins: northern, south-eastern, and south-western. Field data underlined: the presence of chemical-biological gradients between the south-western basin and the rest of the lake and the propagation of a fresher water-plume (formed by the two main northern inflows) into the northern basin and then into the south-western closed arm. The use of a three-dimensional hydrodynamic model showed a periodic movement of this plume that tends to enter the south-western basin first and then to return toward north, moving forward and back through the junction of the three arms. The entrance into the eastern basin, instead, occurs only secondarily. Wavelet transform analysis revealed common periodicity between the plume movement and the action of different external and internal lake-stressors, including: the discharge of the main inflow (period centered at 1, 3.3, and 6.5 day), the wind intensity (0.5 and 1 day) and the two main basin-scale internal wave motions: (3.3 day and 7.1 day). The periodic movement of the fresher water-plume enhances the water exchange and reduces the chemical-biological gradients between the western closed basin and the main lake, playing a crucial role in distributing both inorganic and organic materials at the lake basin-scale.

Water and microbial monitoring technologies towards the near future space exploration.

Space exploration is demanding longer lasting human missions and water resupply from Earth will become increasingly unrealistic. In a near future, the spacecraft water monitoring systems will require technological advances to promptly identify and counteract contingent events of waterborne microbial contamination, posing health risks to astronauts with lowered immune responsiveness. The search for bio-analytical approaches, alternative to those applied on Earth by cultivation-dependent methods, is pushed by the compelling need to limit waste disposal and avoid microbial regrowth from analytical carryovers. Prospective technologies will be selected only if first validated in a flight-like environment, by following basic principles, advantages, and limitations beyond their current applications on Earth. Starting from the water monitoring activities applied on the International Space Station, we provide a critical overview of the nucleic acid amplification-based approaches (i.e., loop-mediated isothermal amplification, quantitative PCR, and high-throughput sequencing) and early-warning methods for total microbial load assessments (i.e., ATP-metry, flow cytometry), already used at a high readiness level aboard crewed space vehicles. Our findings suggest that the forthcoming space applications of mature technologies will be necessarily bounded by a compromise between analytical performances (e.g., speed to results, identification depth, reproducibility, multiparametricity) and detrimental technical requirements (e.g., reagent usage, waste production, operator skills, crew time). As space exploration progresses toward extended missions to Moon and Mars, miniaturized systems that also minimize crew involvement in their end-to-end operation are likely applicable on the long-term and suitable for the in-flight water and microbiological research.

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.

Remediation of internal phosphorus loads with modified clays, influence of fluvial suspended particulate matter and response of the benthic macroinvertebrate community.

Clay-based phosphorus (P) sorbents have been increasingly used as geoengineering materials for the management sediment-derived internal P loading in eutrophic lakes. However, the long-term behavior of these sorbents has remained elusive along with their response to burial under suspended particulate matter (SPM), and their effect on macroinvertebrate communities occupying dynamic regions at the sediment-water interface of shallow and turbid lakes. In this study, field mesocosm experiments were undertaken in Lake Chaohu, China, to study the effects of the application of lanthanum-modified bentonite (LMB) and thermally-modified calcium-rich attapulgite (TCAP) on sediment internal P loading and to assess their influence on macroinvertebrate community structure. A complementary laboratory core incubation study was also undertaken to investigate the effects of SPM deposition on LMB and TCAP performance. In the field, both LMB and TCAP effectively intercepted P released from sediment for up to five months. A P fractionation analysis indicated that LMB and TCAP application results in a substantial increase in inert P fractions in sediment. Laboratory studies indicated that deposition of SPM may increase in mobile P both in the upper sediment and across the new post-SPM deposition sediment-water interface. Importantly, a comparison of sediment chemical extractions and estimated P fluxes suggests that chemically-defined forms of P in the sediment may be used as a proxy to estimate the net sediment P flux. Significantly, the surficial application of either LMB or TCAP did not cause negative effects on macroinvertebrate communities. This study indicates that to sustain a low P flux across the sediment-water interface in shallow, turbid lakes, repeat dosing of geoengineering materials, temporally aligned to the deposition of fluvial SPM, may be required.

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.

Variability of microcystin cell quota in metapopulations of Planktothrix rubescens: causes and implications for water management.

In this study, we investigated the relationships between microcystin (MCs) concentrations and the biovolumes of Planktothrix rubescens (BPr) in 2 natural lakes (Pusiano and Garda) and 2 artificially dammed reservoirs (Occhito and Ledro) in Italy. In all the considered water bodies, P. rubescens was the dominant cyanobacterium. All the lakes were characterized by significant relationships between MCs and BPr, with limited variability in the MC quota (the content of MCs per unit of biovolume) within each water body compared with the variability between sites. The results were consistent with the development of specific MC-genotypes, with moderate seasonal and spatial changes in the proportion between toxic and non-toxic strains. The MC cell quota obtained in our work (ECQ, Environmental Cell Quota) were in the same range of values computed on the basis of analyses made on environmental samples dominated by P. rubescens or Planktothrix agardhii, and on isolates of the same two species (<1 to over 10 µg mm(-3)). Besides the usual ordinary least square regressions, models have been evaluated by using quantile regression, a method that allows estimating the conditional median or other quantiles of the response variable. We showed that the use of quantile regressions has different advantages, which included the computation of MC quota based on the whole range of available data, the robustness against outliers, and the ability to estimate models also in cases where there is no or only weak relationships. The highest ECQ values estimated from 95% quantile regressions in specific water bodies might be used to estimate the worst-case MC concentrations from algal abundances. Nevertheless, it was stressed that a realistic assessment of toxicity and potential adverse health effects necessarily should take into account the toxicity potential of the more abundant MC-congeners produced by specific cyanobacteria populations.

Modelos não-lineares para a estimativa da produção de tomate do tipo cereja / Nonlinear models for estimating cherry tomato yield

RESUMO: Os objetivos do trabalho foram ajustar modelos de regressão não-linear para a estimativa da produção de frutos de tomate tipo cereja e identificar o tamanho da parcela com melhor poder de explicação e ajuste dos modelos, utilizando dois ensaios de uniformidade em estufa plástica. Os modelos ajustados foram o logístico e o de von Bertalanffy, para peso médio de frutos, número médio de frutos e de cachos acumulado nas múltiplas colheitas e com diferentes tamanhos de parcela. Os modelos apresentaram estimativas semelhantes entre si e as mesmas estimativas dos parâmetros em todos os casos de tamanho de parcela. Os modelos de regressão não-linear estudados descrevem satisfatoriamente o comportamento da produção de frutos de tomate tipo cereja cultivado em estufa plástica. Parcela constituída de duas plantas para ensaios em estufa plástica de 250m2 e de três plantas em estufa plástica de 200m2 proporcionam bom poder de explicação nas estimativas dos parâmetros dos modelos.

ABSTRACT: The aim of this paper was to test nonlinear regression models for estimating the cherry tomato production and to identify the plot size with better fitting quality and adjustment of the models, using two uniformity trials in greenhouse. The logistic and von Bertalanffy models were used on variables, as the means fruit weight, the means number of fruits and bunches accumulated in the multiple harvests and with different plot sizes. The models presented similar estimates for all parameters in all plot sizes studied. The nonlinear models adequately describe the behavior of the production of cherry tomato fruits cultivated in greenhouse. Plots constituted by two and three plants, respectively in trials with greenhouse of 250 m2 and 200 m2, provide a good fitting quality in the models adjustment.