Groundwater-dependent ecosystems as transfer vectors of nitrogen from the aquifer to surface waters in agricultural basins: The fontanili of the Po Plain (Italy).

The most spread groundwater-dependent ecosystems in the River Po valley are semi-natural lowland springs called "fontanili". They provide specific habitats and support high biodiversity, but are often strongly impaired by agricultural pollution. In the present study we seasonally monitored the discharge and nitrogen concentration of 48 fontanili from the Adda and the Ticino river basins. We observed a wide spatial variability of both NO3-N concentrations and flows. The annual NO3-N loads ranged from <1 to 75 t y-1 and < 1 to 29 t y-1 in the Adda and Ticino basins respectively. In the springs characterized by variable discharge the N loads were exported mostly during the summer season when water table level was elevated mainly due to irrigation. Upscaling the mean NO3-N load to each river catchment based on the total number of springs, we obtained an aerial export of 33.2 ± 6.0 and 12.5 ± 3.2 kg y-1 ha-1. Such loads accounted for the 30.4 and 21.5% of the N surplus estimated for the Adda and Ticino basins respectively. Random Forest analysis was performed to identify the most important environmental variables influencing the nitrate contamination in the spring waters. A total of 22 explanatory variables related to N sources, land uses, intrinsic hydrogeologic and soil proprieties, in "situ" and remotely sensed variables were considered. The percent of soil cultivated with maize in a 500 m radius buffer area surrounding the sampling site, the N from manure and the distance of each spring from the main river were the most effective factors in controlling the NO3-N concentration in the fontanili water. The outcomes of this work open up to achievable management prospects for the protection and recovery of fontanili waters, and can be particularly useful for water managers in identifying areas and sites where restoration plans should be a priority.

A critical assessment of widely used techniques for nitrate source apportionment in arid and semi-arid regions.

The assessment of nitrate pollution origin using stable isotope techniques is a fundamental prerequisite for the application of sustainable groundwater management plans. Although nitrate pollution is a worldwide groundwater quality problem, existing knowledge on the origin of nitrate pollution in arid and semi-arid regions is still scarce. Using the example of the Grombalia aquifer (NE Tunisia), this work summarizes the main strengths and constraints of multi-isotope techniques targeting at nitrate source identification and apportionment The results highlighted that, even in the case of well-established methodologies, like those of isotope hydrogeochemistry (δ15NNO3, δ 18ONO3 and δ 11B) and mixing modelling for source apportionment, it is fundamental to take into account regional and local end-members to avoid biased data interpretation and to fully exploit the potential of such accurate tools.

C-reactive protein is directly related to plasminogen activator inhibitor type 1 (PAI-1) levels in diabetic subjects with the 4G allele at position -675 of the PAI-1 gene.

BACKGROUND AND AIMS: C-reactive protein (CRP) has been identified as a possible factor able to promote atherosclerosis. "In vitro" studies have demonstrated that CRP induces plasminogen activator inhibitor type 1 (PAI-1) expression, suggesting a hypofibrinolytic role for CRP. As CRP and PAI-1 levels increase in type 2 diabetic subjects, we decided to study the relationship between CRP and PAI-1, and the role of the 4G/5G polymorphism of the PAI-1 gene on this relationship in a diabetic population without complications. METHODS AND RESULTS: Two hundred and ninety-five type 2 diabetic patients (age 60.9+/-10.5 years) and 290 healthy controls (age 59.2+/-11.5 years) were enrolled. A significant correlation between PAI-1 and CRP in diabetic subjects was found (r=0.45, p<0.001), whereas no relationship was evident in the control subjects between these inflammatory markers. Multiple regression analysis highlighted that CRP is the only one significant variable of PAI-1 antigen in diabetic subjects (partial r=0.31, p<0.01). Stratifying by genotype, a positive correlation between PAI-1 and CRP in 4G/4G (partial r=0.64 p<0.001) and 4G/5G (partial r=0.47, p<0.001) subjects was found, whereas no correlation in 5G/5G was present. Multiple regression analysis confirmed the presence of this correlation in 4G/4G (partial r=0.45, p<0.001) and in 4G/5G (partial r=0.34, p=0.007) diabetic patients. CONCLUSIONS: These findings demonstrate that CRP plays an important role in the complex mechanism regulating PAI-1 antigen in 4G diabetic carriers.

Tackling the salinity-pollution nexus in coastal aquifers from arid regions using nitrate and boron isotopes.

Salinization and nitrate pollution are generally ascertained as the main issues affecting coastal aquifers worldwide. In arid zones, where agricultural activities also result in soil salinization, both phenomena tend to co-exist and synergically contribute to alter groundwater quality, with severe negative impacts on human populations and natural ecosystems' wellbeing. It becomes therefore necessary to understand if and to what extent integrated hydrogeochemical tools can help in distinguishing among possible different salinization and nitrate contamination origins, in order to provide adequate science-based support to local development and environmental protection. The alluvial plain of Bou-Areg (North Morocco) extends over about 190 km2 and is separated from the Mediterranean Sea by the coastal Lagoon of Nador. Its surface is covered for more than 60% by agricultural activities, although the region has been recently concerned by urban population increase and tourism expansion. All these activities mainly rely on groundwater exploitation and at the same time are the main causes of both aquifer and lagoon water quality degradation. For this reason, it was chosen as a case study representative of the typical situation of coastal aquifers in arid zones worldwide, where a clear identification of salinization and pollution sources is fundamental for the implementation of locally oriented remedies and long-term management strategies. Results of a hydrogeochemical investigation performed between 2009 and 2011 show that the Bou-Areg aquifer presents high salinity (often exceeding 100 mg/L in TDS) due to both natural and anthropogenic processes. The area is also impacted by nitrate contamination, with concentrations generally exceeding the WHO statutory limits for drinking water (50 mg/L) and reaching up to about 300 mg/L, in both the rural and urban/peri-urban areas. The isotopic composition of dissolved nitrates (δ15NNO3 and δ18ONO) was used to constrain pollution drivers. The results indicate two main origins for human-induced pollution: (i) manure and septic effluents, especially in urban areas, and (ii) synthetic fertilizers in agricultural areas. In the latter, δ15N-enriched values highlight a mixture of those sources, possibly related to unbalanced fertilization and agricultural return flow. Boron isotopes (δ11B) were hence studied to further distinguish the nitrate origin in the presence of multiple sources and mixing processes. The results indicate that in the study area, the high geochemical background for B and Cl, associated to the complex water-rock interaction processes, limit the application of the coupled δ11B and δ15N isotopic systematics to the detection of sources of groundwater pollution. In fact, despite the exceedingly high nitrate contents, the depleted δ11B values that characterize synthetic fertilizers and sewage leakages could not be detected. Therefore, even if in saline groundwater the anthropogenic contribution has a negligible effect in terms of salinity input, with both sewage and irrigation water not very charged, the associated nitrate content fuels up water-rock interaction processes, eventually leading to a mineralization increase.

Integrated socio-hydrogeological approach to tackle nitrate contamination in groundwater resources. The case of Grombalia Basin (Tunisia).

Nitrate contamination still remains one of the main groundwater quality issues in several aquifers worldwide, despite the perduring efforts of the international scientific community to effectively tackle this problem. The classical hydrogeological and isotopic investigations are obviously of paramount importance for the characterization of contaminant sources, but are clearly not sufficient for the correct and long-term protection of groundwater resources. This paper aims at demonstrating the effectiveness of the socio-hydrogeological approach as the best tool to tackle groundwater quality issues, while contributing bridging the gap between science and society. An integrated survey, including land use, hydrochemical (physicochemical parameters and major ions) and isotopic (δ15NNO3 and δ18ONO3) analyses, coupled to capacity building and participatory activities was carried out to correctly attribute the nitrate origin in groundwater from the Grombalia Basin (North Tunisia), a region where only synthetic fertilizers have been generally identified as the main source of such pollution. Results demonstrates that the basin is characterized by high nitrate concentrations, often exceeding the statutory limits for drinking water, in both the shallow and deep aquifers, whereas sources are associated to both agricultural and urban activities. The public participation of local actors proved to be a fundamental element for the development of the hydrogeological investigation, as it permitted to obtain relevant information to support data interpretation, and eventually guaranteed the correct assessment of contaminant sources in the studied area. In addition, such activity, if adequately transferred to regulators, will ensure the effective adoption of management practices based on the research outcomes and tailored on the real needs of the local population, proving the added value to include it in any integrated investigation.

Assessment of groundwater pollution from ash ponds using stable and unstable isotopes around the Koradi and Khaperkheda thermal power plants (Maharashtra, India).

The impact on local water resources due to fly ash produced in the Koradi and Khaperkheda thermal power plants (district of Nagpur, Maharashtra - India) and disposed in large ponds at the surface was assessed through the study of environmental variation of ratios of stable and unstable isotopes. Analyses of oxygen and hydrogen isotopes suggest scarce interaction between the water temporarily stored in the ponds and the groundwater in the study area. Data also highlight that the high salinity of groundwater measured in the polluted wells is not due to evaporation, but to subsequent infiltration of stream waters draining from the ponds to the local aquifer. (87)Sr/(86)Sr values, when associated with Sr/Ca ratios, demonstrate the dominant role of waste waters coming from tens of brick kilns surrounding the pond sulfate pollution. Uranium isotopic analyses clearly show evidence of the interaction between groundwater and aquifer rocks, and confirm again the low influence of ash ponds. A new conceptual model based on the study of the isotopes of radium is also proposed and used to estimate residence times of groundwater in the area. This model highlights that high salinity cannot be in any case attributed to a prolonged water-rock interaction, but is due to the influence of untreated waste water of domestic or brick kiln origin on the shallow and vulnerable aquifers.

Protein S mRNA in patients with protein S deficiency.

A protein S gene polymorphism, detectable by restriction analysis (BstXI) of amplified exonic sequences (exon 15), was studied in seven Italian families with protein S deficiency. In the 17 individuals heterozygous for the polymorphism the study was extended to platelet mRNA through reverse transcription, amplification and densitometric analysis. mRNA produced by the putative defective protein S genes was absent in three families and reduced to a different extent (as expressed by altered allelic ratios) in four families. The allelic ratios helped to distinguish total protein S deficiency (type I) for free protein S deficiency (type IIa) in families with equivocal phenotypes. This study indicates that the study of platelet mRNA, in association with phenotypic analysis based upon protein S assays in plasma, helps to classify patients with protein S deficiency.

The genetic defect of type I von Willebrand disease "Vicenza" is linked to the von Willebrand factor gene.

Type I von Willebrand disease (vWD) Vicenza is a rare variant with autosomal dominant transmission, characterized by the presence of supranormal von Willebrand factor (vWF) multimers in plasma, similar to those normally found in endothelial cells and megakaryocytes. The patients have very low levels of plasma vWF contrasting with a mild bleeding tendency. The pathophysiology of this subtype is still unknown. The presence of supranormal multimers in the patients' plasma could be due to a mutation in the vWF molecule which affects post-translational processing, or to a defect in the cells' processing machinery, independent of the vWF molecule. In order to determine if type I vWD Vicenza is linked to the vWF gene, we studied six polymorphic systems identified within the vWF gene in two apparently unrelated families with type I vWD Vicenza. The results of this study indicate a linkage between vWF gene and the type I vWD Vicenza trait. This strongly suggests that type I vWD Vicenza is due to a mutation in one of the vWF alleles, which results in an abnormal vWF molecule that is processed to a lesser extent than normal vWF.

Resistance to activated protein C in nine thrombophilic families: interference in a protein S functional assay.

Nine thrombophilic patients who had had previous diagnoses of functional protein S deficiency were reinvestigated. The functional protein S assays gave dose-response curves that were not parallel to those of the reference plasma. The same pattern was true for approximately half of the first-degree relatives of the propositi. When protein S was extracted from the plasma of the patients by immunoabsorption, it had a normal ratio of functional activity to immunologic concentration. Restriction fragment length polymorphism analysis, informative in one family, showed no linkage between the protein S gene marker and the abnormal behavior of the protein S functional assay. All the propositi and 23/36 first-degree relatives were resistant to the prolongation of activated partial thromboplastin time induced by activated protein C. Furthermore, there was striking concordance in all patients and relatives between the abnormal pattern of the protein S functional assay and resistance to activated protein C. We conclude that a plasma-based functional protein S assay is sensitive to activated protein C resistance and this may lead to spuriously low results in the assay. In agreement with the results of others, this study indicates that resistance to activated protein C is a frequent hemostatic defect in selected thrombophilic populations.

Intravenous and subcutaneous administration of desmopressin (DDAVP) to hemophiliacs: pharmacokinetics and factor VIII responses.

When desmopressin (DDAVP) is given to mild and moderate hemophiliacs intravenously (i.v.) or subcutaneously (s.c.), there is a very large between-patient variability for peak levels of factor VIII coagulant activity (VIII:C). To evaluate whether or not between-patient variability is related to DDAVP levels achieved in plasma, we measured drug levels in 14 hemophilic volunteers (VIII:C 2 to 31 U/dL) who were randomly given 0.3 micrograms/Kg of i.v. or s.c. DDAVP and crossed-over to the other treatment after an interval of 15-30 days. Peak DDAVP levels (Cmax) were higher for i.v. DDAVP (p less than 0.02), times to peak levels (tmax) were shorter for i.v. DDAVP (p less than 0.001). There was no difference between the i.v. and s.c. routes for plasma DDAVP time curve (AUC) and half-life (t 1/2), but there was much larger variability for pharmacokinetic parameters with i.v. than with s.c. DDAVP. Post-DDAVP VIII:C increased 3.4 +/- 1.6 fold (i.v.) and 3.3 +/- 1.3 fold (s.c.) over baseline levels, with no significant correlation between peak VIII:C and DDAVP levels for either route of administration. These findings establish the s.c. route of DDAVP administration to be bioequivalent in effect to the i.v. route, albeit with less variability. At the DDAVP dosage used in this study and currently recommended for therapy, the VIII:C response is neither a function of the rate of absorption of the compound nor of the magnitude of its plasma concentration.

Plasma factor VII levels are influenced by a polymorphism in the promoter region of the FVII gene.

Genetic factors play a role in determining the variability of plasma factor VII (FVII) levels in healthy individuals. There is also evidence that high serum lipids are associated with high FVII levels in plasma. In the promoter region of the human FVII a DNA polymorphism has been described, originating from a decanucleotide insert present in the less frequent allele. This biallelic system, reflecting the absence (AA) or presence (Aa) of the decanucleotide, can be detected by a DNA enzyme immunoassay of PCR products. We evaluated the association between the polymorphic alleles and the levels of FVII:Ag and FVII:C in 100 healthy individuals and in 19 hypertriglyceridemic individuals. Among healthy individuals, mean FVII:Ag and FVII:C levels of those with the homozygous genotype (A/A; mean FVII:Ag 112%, mean FVII:C 109%) were significantly higher (P < 0.001) than the mean levels of those with the heterozygous genotype (A/a, mean FVII:Ag 80%, mean FVII:C 90%; P < 0.001). Similar genotype-associated differences for FVII:Ag and FVII:C were found in individuals with triglycerides above 250 mg/dl (P < 0.05). FVII:C and FVII:Ag levels were positively related to triglycerides only in individuals without the insert (P < 0.01); there was no significant relationship in those carrying the allele with the insert (A/a; P = 0.43 and 0.08). Our findings of genotype-associated differences in FVII levels and interactions with triglycerides are similar to those obtained with the amino acid dimorphism at position 353 of the factor VII protein.

HELLP syndrome and factor V Leiden.

The association of thrombophilia and obstetrical complications is documented and well consistent with the hypothesis of an insufficient placental perfusion due to fibrin deposition as a major underlying pathophysiological mechanism. Factor V Leiden is one of the most frequent thrombophilic mutations. A high prevalence of this mutation has recently been reported in a group of 21 German women with haemolysis, elevated liver enzymes, low platelets (HELLP) syndrome. In this respect, we studied the prevalence of factor V Leiden in 18 women who were consecutively diagnosed at our Department of Obstetrics and Gynaecology as having HELLP syndrome, between 1995 and 1999. Women were tested either at the time of diagnosis or months or years after delivery for coagulation parameters, protein C (PC), protein S (PS), antithrombin III, lupus-like anticoagulant, anticardiolipin antibodies (ACA), activated protein C (APC) resistance and detection of the G1691A mutation (factor V Leiden). In all women, the parameters studied were normal and in none of the investigated cases was the G1691A mutation found. HELLP being a severe form of preeclampsia, we think that the reported association between factor V Leiden and HELLP may reflect the well-known association with preeclampsia.

Multivariate statistical and GIS-based approach to identify heavy metal sources in soils.

The knowledge of the regional variability, the background values and the anthropic vs. natural origin for potentially harmful elements in soils is of critical importance to assess human impact and to fix guide values and quality standards. The present study was undertaken as a preliminary survey on soil contamination on a regional scale in Piemonte (NW Italy). The aims of the study were: (1) to determine average regional concentrations of some heavy metals (Cr, Co, Ni, Cu, Zn, Pb); (2) to find out their large-scale variability; (3) to define their natural or artificial origin; and (4) to identify possible non-point sources of contamination. Multivariate statistic approaches (Principal Component Analysis and Cluster Analysis) were adopted for data treatment, allowing the identification of three main factors controlling the heavy metal variability in cultivated soils. Geostatistics were used to construct regional distribution maps, to be compared with the geographical, geologic and land use regional database using GIS software. This approach, evidencing spatial relationships, proved very useful to the confirmation and refinement of geochemical interpretations of the statistical output. Cr, Co and Ni were associated with and controlled by parent rocks, whereas Cu together with Zn, and Pb alone were controlled by anthropic activities. The study indicates that background values and realistic mandatory guidelines are impossible to fix without an extensive data collection and without a correct geochemical interpretation of the data.

Gamma dose rate calculation and mapping of piemonte (North-West Italy) from gamma spectrometry soil data.

In this study the air gamma dose rate map of Piemonte, a region in the North-West of Italy, was produced from gamma spectrometry soil data. Soil samples collected in 110 different sites of Piemonte were analysed with Hyperpure Germanium (HPGe) detectors (30% relative efficiency), which allow the evaluation of the activity concentrations of natural radionuclides and (137)Cs. Then, using the available mathematical models, the gamma absorbed dose rate in air due to radionuclides was calculated. The contribution of the cosmic radiation to the total absorbed dose rate, which depend on the site altitude was also evaluated and added to the soil contribution. Finally, the map of the whole region was obtained by fitting the dose rate values of the different sites with kriging algorithms.

[A rare case of choledochocele associated with calculosis of the gallbladder]. / Un raro caso di coledococele associato a calcolosi della colecisti.

The authors report their experience of a case of choledochocele (choledochal cyst) with stones, associated with a gallstone. The exceptional observation diagnosed before the operation node it possible to program total removal of the cyst.

Nitrogen inputs to a river course in a heavily impacted watershed: a combined hydrochemical and isotopic evaluation (Oglio River Basin, N Italy).

This study aims at evaluating sources and processes affecting NO3(-) concentrations in the Oglio River. Five sampling campaigns considered the main watercourse, tributaries, point pollution sources, springs, and groundwater. Physico-chemical parameters, N forms, B, Sr(2+), stable isotopes (δ(2)HH2O, δ(18)OH2O, δ(15)NNO3, δ(18)ONO3, δ(11)B) and discharge were measured. Hydrological modelling was performed using mass balance and End Member Mixing Analysis equations. During the irrigation period, in the upstream reach, up to 90% of the natural river flow is diverted for irrigation and industrial purposes; excess water drained from agricultural fields is returned to river in the downstream reach. Results evidenced, in the middle reach, a large input of NO3(-)-rich groundwater which could be quantified using hydrological modelling. Groundwater inputs are responsible for the sharp, tenfold increase in NO3(-) in the river water, from 2.2-4.4 up to 33.5 mgL(-1), and are more evident in summer, when discharge is lower. Nevertheless, river water preserves its natural B isotopic composition, indicating that the two tracers do not have a common origin and are not co-migrant. In the lower plain, surface-groundwater interconnections and human disturbances in the water cycle favour the recycling of the compounds in the environment, and lead to a similarity in composition of the different water bodies (Oglio River, tributaries and groundwater). The long lasting agronomical practices have profoundly modified the surface-groundwater equilibrium and chemical characteristics, resulting in a highly buffered system. Infiltrating irrigation water leaches down NO3(-) which is subsequently denitrified; when returned to the Oglio River, groundwater modifies the river water composition by dilution, in the case of NO3(-), or by addition, for other constituents (e.g. Cl(-), B). The results of this study indicate that, in order to reduce the NO3(-) transport towards the Adriatic Sea, groundwater contamination should be addressed first, with expected long recovery times.

Identifying the effects of human pressure on groundwater quality to support water management strategies in coastal regions: a multi-tracer and statistical approach (Bou-Areg region, Morocco).

Groundwater pollution from anthropogenic sources is a serious concern affecting several coastal aquifers worldwide. Increasing groundwater exploitation, coupled with point and non-point pollution sources, are the main anthropogenic impacts on coastal environments and are responsible for severe health and food security issues. Adequate management strategies to protect groundwater from contamination and overexploitation are of paramount importance, especially in arid prone regions, where coastal aquifers often represent the main freshwater resource to sustain human needs. The Bou-Areg Aquifer (Morocco) is a perfect example of a coastal aquifer constantly exposed to all the negative externalities associated with groundwater use for agricultural purposes, which lead to a general increase in aquifer salinization. In this study data on 61 water samples, collected in June and November 2010, were used to: (i) track groundwater composition changes related to the use of irrigation water from different sources, (ii) highlight seasonal variations to assess aquifer vulnerability, and (iii) present a reproducible example of multi-tracer approach for groundwater management in rural coastal areas. Hydrogeochemical results show that Bou-Areg groundwater is characterized by - high salinity, associated with a remarkable increase in bicarbonate content in the crop growing season, due to more intense biological activity in irrigated soils. The coupled multi-tracer and statistical analysis confirms the strong dependency on irrigation activities as well as a clear identification of the processes governing the aquifer's hydrochemistry in the different seasons. Water Rock Interaction (WRI) dominates the composition of most of groundwater samples in the Low Irrigation season (L-IR) and Agricultural Return Flow (ARF) mainly affects groundwater salinization in the High Irrigation season (H-IR) in the same areas naturally affected by WRI. In the central part of the plain River Recharge (RR) from the Selouane River is responsible for the high groundwater salinity whilst Mixing Processes (MIX) occur in absence of irrigation activities.

Impact of the disposal and re-use of fly ash on water quality: the case of the Koradi and Khaperkheda thermal power plants (Maharashtra, India).

An increasing amount of fly ash from thermal power plants is produced in India every year. Its disposal is generally done in ponds after it is mixed together in suitable proportion of water to form a slurry. Fly ash from Koradi and Khaperkheda thermal power plants (Nagpur, Maharashtra) is commonly disposed in an area characterized by the presence of many small villages where the population uses the groundwater for drinking and domestic purposes. Here, the groundwater locally exceeds the concentration limits recommended by the Bureau of Indian Standards (BIS, 2005) and by the World Health Organization (WHO, 2008) for Mg(2+), Ca(2+), NO3(-), SO4(2-), Total Dissolved Solids (TDS) and for some minor elements like As, Mo, V and U. A new geological map of the study area has been prepared to understand the possible water-rock interactions. An extensive geochemical survey of groundwater, stream water and fly ash was also carried out to clarify the possible origin of the pollutants by discriminating between geogenic and anthropogenic sources and to assess the influence of the ash ponds on water quality. The analytical results suggest that a large part of the sulfates in the groundwater of the villages of Masada, Khairi and Kawatha originate from the infiltration of industrial water from tens of factories that mix fly ash with relatively high quantities of gypsum and lime for the production of bricks. In addition, the interaction with the relatively U-rich Gondwana units, like Talchir formation, is probably the cause of the high concentration of this element. Results showed how the relatively high concentrations of Mo, As, B and F in circulating waters are linked to the leaching from fly ash, also pointing out a direct spatial correlation between the concentration of fluorides in the groundwater and their closeness to the ash ponds.