Effects of aquifer thermal energy storage on groundwater quality and the consequences for drinking water production: a case study from The Netherlands.

We used data from an aquifer thermal energy storage (ATES) system located 570 m from a public water supply well field in the south of The Netherlands to investigate the relation between production of renewable energy with an ATES system and the production of drinking water. The data show that the groundwater circulation by the ATES system can impact chemical groundwater quality by introducing shallow groundwater with a different chemical composition at greater depth. However, the observed concentration changes are sufficiently small to keep groundwater suitable for drinking water production. Microbiological results showed that the ATES system introduced faecal bacteria in the groundwater and stimulated the growth of heterotrophic micro-organisms. At the studied site this forms no hygienic risk because of the long distance between the ATES wells and the public supply well field A further degradation of either chemical or microbiological groundwater quality however may necessitate additional water treatment which raises the energy requirements. The additional energy requirements for drinking water treatment may be up the same order of magnitude as the harvested energy by the ATES system.

Geochemistry of trace metals in a fresh water sediment: field results and diagenetic modeling.

Concentrations of Fe, Mn, Cd, Co, Ni, Pb, and Zn were determined in pore water and sediment of a coastal fresh water lake (Haringvliet Lake, The Netherlands). Elevated sediment trace metal concentrations reflect anthropogenic inputs from the Rhine and Meuse Rivers. Pore water and sediment analyses, together with thermodynamic calculations, indicate a shift in trace metal speciation from oxide-bound to sulfide-bound over the upper 20 cm of the sediment. Concentrations of reducible Fe and Mn decline with increasing depth, but do not reach zero values at 20 cm depth. The reducible phases are relatively more important for the binding of Co, Ni, and Zn than for Pb and Cd. Pore waters exhibit supersaturation with respect to Zn, Pb, Co, and Cd monosulfides, while significant fractions of Ni and Co are bound to pyrite. A multi-component, diagenetic model developed for organic matter degradation was expanded to include Zn and Ni dynamics. Pore water transport of trace metals is primarily diffusive, with a lesser contribution of bioirrigation. Reactions affecting trace metal mobility near the sediment-water interface, especially sulfide oxidation and sorption to newly formed oxides, strongly influence the modeled estimates of the diffusive effluxes to the overlying water. Model results imply less efficient sediment retention of Ni than Zn. Sensitivity analyses show that increased bioturbation and sulfate availability, which are expected upon restoration of estuarine conditions in the lake, should increase the sulfide bound fractions of Zn and Ni in the sediments.

Potential kinetic availability of metals in sulphidic freshwater sediments.

The insolubility of metal sulphides is believed to limit the bioavailability of trace metals in sulphidic sediments. However, if non-equilibrium conditions are important, metals may be more available than simple thermodynamic calculations suggest. To investigate the possible dynamic supply of Cu, Ni and Zn in a sulphidic freshwater sediment, they were measured, along with iron, manganese and sulphide, by the technique of diffusive gradients in thin-films (DGT). DGT measures the supply of solute from sediment to solution in response to a local solute sink. Release of Mn, Cu, Zn and Ni was observed at the sediment surface and attributed to the supply from reductive dissolution of manganese oxides. The depth profile of simultaneously extractable metals (SEM) for Cu and Ni followed the shape of the Mn profile more closely than the profiles of either acid volatile sulphur (AVS) or Fe, again consistent with supply from Mn oxides. Solubility calculations for a mesocosm of homogenised sediment indicated supersaturation with respect to the sulphides of Fe, Cu, Ni and Zn, yet DGT measurements demonstrated a substantial supply of both trace metals and sulphide from the solid phase to the pore waters. Ratios of metals measured in pore waters by DGT were consistent with their release from iron and manganese oxides, indicating that supply, as much as removal processes, determines the pseudo-steady state concentrations in the pore waters. The observations suggest that trace metals are not immediately bound in an insoluble, inert form when they are in contact with sulphide. This has consequences for modelling metal processes in sediment, as well as for uptake by some biota.

Catabolism of polyamines in the rat. Polyamines and their non-alpha-amino acid metabolites.

The metabolic fate of stable isotopically labeled polyamines was investigated after their first and second intraperitoneal injection in rats. Using gas chromatographic and mass fragmentographic analyses of acid-hydrolyzed 24-h urines, some aspects of the polyamine metabolism could be elucidated. After the injections with hexadeutero-1,3-diaminopropane, only labeled 1,3-diaminopropane was recovered from the urine samples. The rat injected with tetradeuteroputrescine excreted labeled putrescine, gamma-amino-n-butyric acid, 2-hydroxyputrescine and spermidine, while the urine samples of the rat after the injections with tetradeuterocadaverine contained labeled cadaverine and delta-aminovaleric acid. The injections of hexadeuterospermidine led to the appearance of labeled spermidine, isoputreanine, putreanine, N-(2-carboxyethyl)-4-amino-n-butyric acid, putrescine, gamma-amino-n-butyric acid, 1,3-diaminopropane, beta-alanine and spermine. After the injections with bis(2-carboxyethyl)-1,4-diaminobutane, spermidine, isoputreanine, putreanine, N-(2-carboxyethyl)-4-amino-n-butyric acid, putrescine, 1,3-diaminopropane, beta-alanine, 2-hydroxyputrescine and possibly gamma-amino-n-butyric acid were recovered. Clear differences between the metabolism after the first and second injection were noted for putrescine, spermidine and spermine, which is suggestive for enzyme induction and/or the existence of salvage pathways.

Urinary polyamine and metabolite excretion by children with Zellweger's syndrome.

In order to investigate whether, due to a lack of peroxisomes, polyamine degradation is altered in patients with the cerebro-hepato-renal syndrome of Zellweger, we determined total, free and acetylated polyamines and some of their catabolites in urines of six patients and age-matched healthy children. The normal polyamine excretion patterns of the patients, compared to the control group, suggest that either the intracellular localisation of the polyamine degrading enzyme, polyamine oxidase, is not exclusively limited to peroxisomes or that the enzyme is located in the peroxisomal matrix.

Determination of pipecolic acid in urine and plasma by isotope dilution mass fragmentography.

A capillary gas chromatographic method with mass spectrometric detection for the determination of pipecolic acid in urine and plasma (or serum) has been developed. Using a quantification based on stable isotope dilution mass fragmentography the concentration of pipecolic acid was determined in urines of 34 healthy children and 8 patients with Zellweger's syndrome. The urinary pipecolic acid excretion of healthy infants decreases with age. Its concentration in urines of patients with Zellweger's syndrome was not consistently elevated. Normal values for pipecolic acid in plasma were established for 19 healthy children. Pipecolic acid concentrations in 47 urine samples (range 0.02-228.3 mmol/mol of creatinine) and 6 serum samples of Zellweger patients after oral loading with DL-pipecolic acid (range 65-1334 mumol/l) were found to correlate satisfactorily with the results obtained by an amino acid analyzer method. The major advantage of the presented method over the amino acid analyzer method concerns its greater sensitivity and its much shorter analysis time.

Determination of polyamines and metabolites in cerebrospinal fluid by isotope dilution mass fragmentography, and a clinical application.

Capillary gas chromatography and mass fragmentography was used to determine simultaneously 1,3-diaminopropane, putrescine, cadaverine, spermidine, spermine, isoputreanine and putreanine in cerebrospinal fluid. After addition of deuterium labelled analogs and acid hydrolysis, the compounds were isolated by adsorption onto silica and converted into their N-heptafluorobutyryl-methylesters. Quality control data and an application of the method are given. A patient harbouring an astrocytoma was monitored during chemotherapeutic treatment.

Urinary polyamines and their metabolites during new combination chemotherapeutic treatments of high grade non-Hodgkin lymphoma.

Nineteen patients with non-Hodgkin lymphoma of unfavourable histology (15 high grade and 4 intermediate grade) were treated with two new combination chemotherapeutic schemes. Except for one all were partial (8) or complete (10) responders to treatment. Polyamines were measured in every spontaneously voided urine sample. Pretherapeutically all (11) stage III and IV patients had borderline or increased urinary putrescine (Pu) and sum of isoputreanine, spermidine and spermine (sigma Isoputr,Sd,Sp), except for the non-responder. Except for one, all (8) stage I and II patients had normal urinary Pu and sigma Isoputr,Sd,Sp. Posttherapeutically patients with pretherapeutically increased sigma Isoputr,Sd,Sp returned to normal (5), borderline (2), or slightly increased (3) levels. The post-therapeutic achievement of normal or borderline sigma Isoputr,Sd,Sp was not necessarily connected with accomplishment of complete remission. From the start of therapy until clinical restaging, partially or completely responding stage III and IV patients excreted 5-234 mmol sigma Isoputr,Sd,Sp per mol of creatinine above the mean normal value plus 2 SD. For stage I and II patients and the clinical non-responder this parameter amounted to 0-5 mmol/mol of creatinine. Peaks in urinary Pu and sigma Isoputr,Sd,Sp follow-up curves were related in time to the administration of chemotherapeutics. For responding stage III and IV patients the rate of the decrease of sigma Isoputr,Sd,Sp levels paralleled the clinically observed rate of tumour load reduction. This study suggests that notably for non-Hodgkin lymphoma patients with high tumour loads the constant monitoring of polyamines can provide information on pretherapeutic spontaneous tumour cell loss, the efficacy of chemotherapeutic combinations, the kinetics-, and (within certain limitations) the extent of therapeutically induced tumour cell death.

Microbial influences on urinary polyamine excretion.

We determined diamines, polyamines, their monoacetylated conjugates and some of their catabolites in urines of healthy persons during decontamination of the gastrointestinal tract and patients with urinary tract infections. The compounds were also measured after in vitro incubation of urines from healthy persons and patients. During decontamination the urinary excretion of total putrescine decreased by a small amount. This fall was for the greater part accountable to monoacetylated putrescine. Free putrescine levels were increased in urines of patients with urinary tract infections, decreased after therapy, and increased after incubation of the pretherapeutical samples. Total cadaverine decreased during decontamination and increased during recontamination. The changes were partly accountable to monoacetylated cadaverine. Free cadaverine levels of patients with urinary tract infections were normal and did not change after therapy. These data show that, under normal conditions, a small part of monoacetylated putrescine and a considerable part of monoacetylated cadaverine originate from the gastrointestinal tract, and that urinary tract infections lead to an increase of free putrescine. The microbial synthesis of putrescine in the gastrointestinal- and urinary tracts, should therefore be taken into account for the interpretation of urinary putrescine levels as a parameter for body cell turnover.

Dredging-related mobilisation of trace metals: a case study in The Netherlands.

Mobilisation of contaminants is an important issue in environmental risk assessment of dredging projects. This study has aimed at identifying the effects of dredging on mobilisation of trace metals (Zn, Cu, Cd and Pb). The intensities and time scales of trace metal mobilisation were investigated during an experimental dredging project conducted under field conditions. The loss of contaminated dredge spoil is mainly reflected by increasing levels of trace metals in the suspended matter, dissolved trace metal concentrations in the water column are not significantly influenced by the dredging activities. This indicates a strong binding mechanism of trace metals to the solid phase or a fast redistribution over sorptive phases in response to oxidation of e.g. trace metal sulphides. Given the differences in levels of reactive phases (Mn, Fe, sulphides and organic matter) between the riverine suspended matter and the sediments, changes in the levels of these parameters in the suspended matter upon dredging may give information on the processes influencing the behaviour of trace metals and on the potential loss of sediment during dredging operations. Therefore, we recommend to routinely measure these parameters in studies on contaminant behaviour related to dredging activities.

Enteropathy-associated T-cell lymphoma presenting with eosinophilia.

Hypereosinophilia can be related to various diseases; when it occurs without an obvious cause it is called idiopathic hypereosinophilic syndrome (IHES). We describe a patient with increasing eosinophilia, which in spite of extensive diagnostic procedures initially remained unexplained. However, during follow-up it became apparent that this patient had a lethal enteropathy-associated T lymphoma (EATL) causing the hypereosinophilia.

Simultaneous release of sulfide with Fe, Mn, Ni and Zn in marine harbour sediment measured using a combined metal/sulfide DGT probe.

The technique of DGT (Diffusive Gradients in Thin Films) was further developed to allow simultaneous measurement of sulfide and trace metals at the same location in sediment. The new combined DGT probe consisted of a layer of gel impregnated with AgI, overlain by (1) a layer of gel containing Chelex, (2) a layer of gel and (3) a filter membrane. Diffusion of sulfide was controlled by layers (1) to (3), while diffusion of metals was controlled by layers (2) and (3). The Chelex gel trapped metals that were measured after elution with acid. The AgI gel trapped sulfide through the formation of Ag2S. This was then measured densitometrically as the colour changed from pale yellow to grey. Experiments demonstrated that concentrations of metal or sulfide measured by the combined device were no different to the concentrations measured by more conventional devices. The presence of Chelex in the gel did not impede the diffusion of sulfide. Deployment of a combined probe in marine sediment revealed simultaneous remobilisation of metals and sulfide at the same location. Solubility calculations indicated that some precipitation of amorphous FeS was probably occurring at the maxima in sulfide concentrations. There was general undersaturation with respect to NiS, but ZnS was supersaturated at all locations. There appeared to be localised active zones of organic matter decomposition, where reduction of manganese oxides, iron oxides and sulfate occurred simultaneously. Mass balance calculations indicated that Ni could not be supplied by release from decomposing organic matter. Manganese oxides were the most likely source, but supply from reductive dissolution of iron oxides could not be entirely discounted. Supply from either Fe or Mn oxides could account for the Zn maxima. Application of the newly developed combined probe provides new information that helps understanding of the complex nature of trace metal and sulfur chemistry in sediments.

Investigation of polyamine metabolism by high-performance liquid chromatographic and gas chromatographic profiling methods.

Measurements of polyamines, polyamine conjugates and their metabolites in tissues, cells and extracellular fluids are used in biochemistry, (micro)biology, oncology and parasitology. Decarboxylation of ornithine yields putrescine. Aminopropylation of putrescine yields spermidine, and aminopropylation of spermidine yields spermine. Spermidine and spermine are retroconverted to putrescine and spermidine, respectively, by initial N-acetylation and subsequent polyamine oxidation. The intermediate N-acetylputrescine, N1-acetylspermidine and N8-acetylspermidine are the major urinary N-acetylpolyamines. Polyamines and N-acetylpolyamines are terminally degraded to non-alpha-amino acid metabolites by oxidative deamination and aldehyde dehydrogenation. Chromatography with on-line detection is the most commonly applied profiling method for polyamines, N-acetylpolyamines and their non-alpha-amino acid metabolites. Cation-exchange and reversed-phase high-performance liquid chromatography require pre- or post-column derivatisation, followed by UV-Vis spectrophotometric or fluorimetric detection. Isolation and derivatisation precedes gas chromatography with flame-ionisation, nitrogen-phosphorus, electron-capture or mass spectrometric detection. High-performance liquid chromatography and gas chromatography of polyamines are not competitive techniques, but rather supplementary.

Determination of N-(3-acetamidopropyl)pyrrolidin-2-one, a metabolite of spermidine, in urine by isotope dilution mass fragmentography.

A capillary gas chromatographic method with mass spectrometric detection for the determination of N-(3-acetamidopropyl)pyrrolidin-2-one, the monoacetyl conjugate of isoputreanine-gamma-lactam, in urine has been developed. Using a quantification based on stable isotope dilution mass fragmentography, age-dependent normal values for the urinary excretion of N-(3-acetamidopropyl)pyrrolidin-2-one by 44 apparently healthy control subjects were determined. Quality control data and normal values for 27 adults are given. The method was applied to the monitoring of the chemotherapeutic treatment of two patients with high-grade non-Hodgkin lymphoma.

Mass fragmentographic identification of polyamine metabolites in the urine of normal persons and cancer patients, and its relevance to the use of polyamines as tumour markers.

The mass fragmentographic identification of N-(2-carboxyethyl)-4-amino-n-butyric acid, N-(3-aminopropyl)-N1-(2-carboxyethyl)-1,4-diaminobutane, N,N1-bis(2-carboxyethyl)-1,4-diaminobutane, and delta-aminovaleric acid in acid-hydrolysed urines of a normal person and two cancer patients is described. A previous study, in which the metabolic fate of intraperitoneally injected polyamines in rats was investigated, revealed that these compounds should be considered as non-alpha-amino acid metabolites of the naturally occurring polyamines. Quantification of polyamines and their non-alpha-amino acid metabolites by gas chromatography with nitrogen--phosphorus detection showed that, relative to the parent polyamines, humans normally excrete higher quantities of polyamine catabolites in urine than rats, suggesting that humans catabolize polyamines more efficiently. As illustrated by the follow-up of the concentrations of polyamines and their catabolites in the urine of a patient with high-grade non-Hodgkin lymphoma during chemotherapy, the catabolic pressure on polyamines may be considerably increased during neoplastic diseases, since an even higher proportion of oxidized polyamine metabolites was observed. It is therefore suggested that the additional measurement of the circulating concentrations of polyamine-degrading enzymes is of importance for the correct interpretation of polyamine (metabolite) determinations for oncological purposes.

Determination of polyamines in human erythrocytes by capillary gas chromatography with nitrogen-phosphorus detection.

A capillary gas chromatographic method with nitrogen-phosphorus detection is used to determine simultaneously 1,3-diaminopropane, putrescine, cadaverine, spermidine and spermine in human erythrocytes. The compounds are isolated by adsorption on silica and converted into their heptafluorobutyryl derivatives. We give quality-control data and (age-dependent) normal values for 48 apparently healthy controls.

Gestational-age-dependent concentrations of polyamines, their conjugates and metabolites in urine and amniotic fluid.

The metabolism and fate of polyamines during cell proliferation, differentiation, and cell loss were investigated by measuring the concentration of polyamines, their conjugates and some of their metabolites in amniotic fluid of 24 subjects, and in urine of 85 women during pregnancy. The increase of putrescine and spermine in acid-hydrolysed urines during pregnancy appeared to be almost completely due to increases in monoacetylated putrescine and N1,N12 diacetylated spermine, respectively. The latter two were the quantitatively most important polyamines in amniotic fluid. In urine, monoacetylated putrescine showed the highest levels at the end of pregnancy, whereas N1,N12 diacetylated spermine reached the highest values at about 32 weeks gestation. It was impossible to establish whether extracellular monoacetylated putrescine is linked either to cell growth or cell loss. The appearance of N1,N12 diacetylated spermine is probably due to cell loss and dependent on the degree of differentiation during fetal development. The decline and eventual disappearance of urinary N1,N12 diacetylated spermine during the first 2 years after birth may be coherent with maturation of the FAD-dependent polyamine oxidase activity.

Gas chromatographic determination of N-acetylisoputreanine-gamma-lactam, a unique catabolite of N1-acetylspermidine.

A capillary gas chromatographic method with nitrogen-phosphorus detection for the determination of N-acetylisoputreanine-gamma-lactam (acisoga) in urine is described. The method was validated by comparing the results with those given by an isotope dilution mass fragmentographic method. Making use of specific inhibitors for copper-dependent amine oxidase and polyamine oxidase in rats, it was demonstrated that acisoga is formed by oxidative deamination of N1-acetylspermidine by the former enzyme. Moreover, acisoga is not a substrate for pig liver polyamine oxidase. Increased concentrations of acisoga, relative to N1-acetylspermidine, in urines of patients with non-Hodgkin's lymphoma indicated that this conversion diminishes the sensitivity of N1-acetylspermidine as a marker for (tumour) cell death.

Simultaneous gas-chromatographic determination of free and acetyl-conjugated polyamines in urine.

A capillary gas-chromatographic method with nitrogen-phosphorus detection is used to determine simultaneously urinary 1,3-diaminopropane, monoacetyl-1,3-diaminopropane, putrescine, monoacetylputrescine, cadaverine, monoacetylcadaverine, spermidine, N1-acetylspermidine, N beta-acetylspermidine, spermine, N1-acetylspermine, isoputreanine, N-(3-aminopropyl)pyrrolidin-2-one, and putreanine. The compounds are isolated by adsorption onto silica and converted into their methyl-heptafluorobutyryl derivatives. We give quality-control data and age-dependent "normal" values for urinary excretion of these analytes from 51 apparently healthy control subjects. Normal values for 31 adults are compared with those reported in the literature. Monoacetyl-1,3-diaminopropane and N1-acetylspermine are identified by mass fragmentography. We applied the method to monitor chemotherapeutic treatment of a patient with advanced non-Hodgkin's lymphoma; we identified by mass spectrometry N1,N12-diacetylspermine in this patient's urine.

Microbial flora in the gastrointestinal tract abolishes cytostatic effects of alpha-difluoromethylornithine in vivo.

Although treatment with the ornithine decarboxylase inhibitor alpha-difluoromethylornithine (DFMO) leads to depletion of intracellular polyamines and to related growth inhibition in vitro, its cytostatic effects in vivo are disappointing. This may be due to abolition of DFMO-induced growth inhibition by polyamines released during normal body cell turnover, to dietary polyamines, or to putrescine synthesized by the microbial flora in the GI tract. We studied selectively (aerobic) and totally (aerobic + anaerobic) GI tract-decontaminated LI210-bearing mice fed with 3 types of diet differing in their polyamine and carbohydrate residue contents and treated with combinations of intraperitoneal DFMO and oral deuterium-labelled putrescine. Our data show that, irrespective of diet type, total decontamination markedly potentiates the moderate tumor growth inhibition that is caused by DFMO alone. During total decontamination, growth-inhibited L1210 cells accumulate in the G0/G1 phase of the cell cycle. Although orally administered deuterium-labelled putrescine gave rise to deuterium labelling of L1210 putrescine, spermidine and spermine, the polyamine levels in our diets played only a minor role.