Response to "Comment on 'Binding Debye-Hückel theory for associative electrolyte solutions'" [J. Chem. Phys. 159, 154503 (2023)].

This Response addresses critiques raised about the Binding Debye-Hückel (BiDH) theory [Naseri Boroujeni et al., J. Chem. Phys. 159, 154503 (2023)] by Simonin and Bernard [J.-P. Simonin and O. Bernard, J. Chem. Phys. (2024)]. The critiques questioned the foundational framework of the Debye-Hückel (DH) theory, the relevance of ion pairing in primitive model fluids, and the accuracy of the BiDH model compared to mean spherical approximation model. Through a systematic rebuttal, supported by extensive literature review and comparison with Monte Carlo simulation data, this Response addresses these concerns. It demonstrates the efficacy of DH theory in describing real electrolyte solutions, validates the relevance of ion pairing in primitive model fluids, and establishes the BiDH model's accuracy in describing electrolyte properties.

Theoretical and practical investigation of ion-ion association in electrolyte solutions.

In this study, we present a new equation of state for electrolyte solutions, integrating the statistical associating fluid theory for variable range interactions utilizing the generic Mie form and binding Debye-Hückel theories. This equation of state underscores the pivotal role of ion-ion association in determining the properties of electrolyte solutions. We propose a unified framework that simultaneously examines the thermodynamic properties of electrolyte solutions and their electrical conductivity, given the profound impact of ion pairing on this transport property. Using this equation of state, we predict the liquid density, mean ionic activity coefficient, and osmotic coefficient for binary NaCl, Na2SO4, and MgSO4 aqueous solutions at 298.15 K. Additionally, we evaluate the molar conductivity of these systems by considering the fraction of free ions derived from our equation of state in conjunction with two advanced electrical conductivity models. Our results reveal that, while ion-ion association has a minimal influence on the modification of the predicted properties of sodium chloride solutions, their impact on sodium and magnesium sulfate solutions is considerably more noticeable.

Binding Debye-Hückel theory for associative electrolyte solutions.

This study presents a new equation of state (EOS) for charged hard sphere fluids that incorporates ion-ion association. The EOS is developed using the Debye-Hückel (DH) theory, reference cavity approximation, and Wertheim's theory. Predictive accuracy is evaluated by comparing the model's predictions with Monte Carlo simulations for various charged hard-sphere fluids. The assessment focuses on mean ionic activity coefficient, individual ionic activity coefficient, and osmotic coefficients. The results demonstrate good agreement between the model and simulations, indicating its success for different electrolyte systems. Incorporating ion-ion association improves accuracy compared to the DH theory. The importance of the cavity function and ion-dipole interactions is emphasized in accurately representing structural properties. Overall, the developed EOS shows promising predictive capabilities for charged hard sphere fluids, providing validation and highlighting the significance of ion-ion association in thermodynamic predictions of electrolyte solutions.

High Mortality from Major Vascular Trauma in Traffic Accidents: A Population-Based Study.

BACKGROUND AND AIMS: Injuries involving major arteries are an important cause of mortality and morbidity, most often from road traffic accidents. Our aim was to study the outcome of major vascular trauma from traffic accidents in an entire population, including patients who die at the scene and those who reach hospital alive. MATERIALS AND METHODS: This was a retrospective analysis of all patients who sustained major vascular trauma in traffic accidents in Iceland from 2000 to 2011. Patient demographics, mechanism, and location of vascular injury and treatment were registered. Injury scores were calculated and overall survival estimated. RESULTS: There were 62 individuals (mean age 44 years, 79% males) with 95 major vascular traumas, giving an incidence of 1.69/100,000 inhabitants (95% confidence interval: 1.27-2.21). A total of 33 died at the scene and 8 during transportation to hospital but 21 (34%) reached hospital alive. Most patients who succumbed had thoracic major vascular traumas (76%) or abdominal major vascular traumas (23%). Mean new injury severity score for the 21 admitted patients was 44. A total of 18 were operated with vascular repair, 3 with endovascular stent graft insertion. The mean hospital stay for discharged patients was 34 days. Altogether, 15 of the 62 patients (24%) survived to discharge from hospital, with a 5-year survival of 86% for discharged patients. CONCLUSION: Every other patient with major vascular trauma following traffic accidents died at the scene and a further 13% died during transportation to hospital, most of whom sustained major vascular trauma to the thoracic aorta. However, one-third of the patients reached hospital alive and 71% of them survived to discharge, with excellent long-term survival.

A population-based study on epidemiology of intensive care unit treated traumatic brain injury in Iceland.

BACKGROUND: Traumatic brain injury is a worldwide health issue and a significant cause of preventable deaths and disabilities. We aimed to describe population-based data on intensive care treated traumatic brain injury in Iceland over 15 years period. METHODS: Retrospective review of all intensive care unit admissions due to traumatic brain injury at The National University Hospital of Iceland 1999-2013. Data were collected on demographics, mechanism of injury, alcohol consumption, glasgow come scale upon admission, Injury Severity Scoring, acute physiology and chronic health evaluation II score, length of stay, interventions and mortality (defined as glasgow outcome score one). All computerized tomography scans were reviewed for Marshall score classification. RESULTS: Intensive care unit admissions due to traumatic brain injury were 583. The incidence decreased significantly from 14/100.000/year to 12/100.000/year. Males were 72% and the mean age was 41 year. Majority of patients (42%) had severe traumatic brain injury. The most common mechanism of injury was a fall from low heights (36.3%). The mortality was 18.2%. Increasing age, injury severity score, Marshall score and acute physiology and chronic health evaluation II score are all independent risk factors for death. Glasgow coma scale was not an independent prognostic factor for outcome. CONCLUSIONS: Incidence decreased with a shift in injury mechanism from road traffic accidents to falls and an increased rate of traumatic brain injury in older patients following a fall from standing or low heights. Mortality was higher in older patients falling from low heights than in younger patients suffering multiple injuries in road traffic accidents. Age, injury severity score, acute physiology and chronic health evaluation II score and Marshall score are good prognostic factors for outcome. Traumatic brain injury continues to be a considerable problem and the increase in severe traumatic brain injury in the middle age and older age groups after a seemingly innocent accident needs a special attention.

The incidence of a first major osteoporotic fracture in Iceland and implications for FRAX.

SUMMARY: Based on an extensive cohort study over 25 years, the present study supports the assumption that major osteoporotic fractures can be reasonably predicted from hip fracture rates. INTRODUCTION: The construct for FRAX models depends on algorithms to adjust for double counting of fracture outcomes in some models and in others, to estimate the incidence of a major fracture from hip fracture rates. The aim of the present study was to test the validity of these algorithms in a large prospective cohort. METHODS: The incidence of hip, clinical spine, distal forearm, and humerus fracture was determined in the prospective and ongoing population-based Reykjavik Study with follow up of 257,001 person-years. The incidence of a first major fracture was compared with the correction factors used in FRAX to adjust the incidence of several fracture outcomes for double counting. In addition, the incidence of a major osteoporotic fracture estimated from the Icelandic hip fracture rates was compared with the Malmo ratios used in FRAX. RESULTS: The adjustments necessary to account for multiple fracture outcomes were similar to those previously derived from Sweden. Additionally, incidence of a first major osteoporotic fracture was similar to that derived for FRAX models. CONCLUSION: The findings of the present study support the algorithms used in FRAX to estimate the incidence of a first major fracture and the predictive value of hip fracture for other major fractures.

Epidemiology of fractures in Iceland and secular trends in major osteoporotic fractures 1989-2008.

UNLABELLED: The incidence of the most common fracture types in Iceland is reported based on individual data from the Reykjavik Study 1967-2008. Time trend is reported for the major osteoporotic fractures (MOS) 1989-2008. INTRODUCTION: This study aims to assess the incidence of all fractures in Iceland, with emphasis on the rate of hip fractures, and compare the incidence with other populations as well as examine the secular changes. METHODS: Individuals from the prospective population-based cohort Reykjavik Study were examined between 1967 and 2008 (follow-up 26.5 years), which consisted of 9,116 men and 9,756 women born in 1907-1935, with age range 31-81 years. First fracture incidence was estimated using life table methods with age as the timescale. RESULTS: Fracture rate increased proportionally with age between the sexes for vertebral and proximal humerus but disproportionally for hip and distal forearm fractures. The ratio of first fracture incidence between the sexes varied considerably by site: 2.65 for hip fractures and the highest for distal forearm fractures at 4.83. By the age of 75, 36.7% of women and 21% of men had sustained a fracture, taking into account competing risk of death. The incidence of hip fractures was similar to results previously published from USA, Sweden, Norway, and Scotland. The incidence of MOS fractures in both sexes decreased over the last decade, except hip fractures in men, which remained unchanged, as reflected in the women/men ratio for the hip, which changed from 2.6 to 1.7. CONCLUSION: This study adds information to scarce knowledge on the relative fracture incidence of different fractures. The incidence of MOS fractures increased in the latter part of the last century in both sexes and declined during the last decade, less dramatically for men. This information is important for planning health resources.

Do we agree about when patients are psychotic?

OBJECTIVE: To investigate into the use of the term 'psychotic' as defined by ICD-10 or by the concept of impaired reality testing, among psychiatric staff members. METHOD: Questionnaire investigation using 11 short case vignettes. RESULTS: Responses were received from 266 psychiatric staff members: psychiatrists, nursing staff and psychologists. When using ICD-10, patients were identified as psychotic with a sensitivity ranging from 90% to 55%. Specificity ranged from 60% to 75%. According to the concept of impaired reality testing, all three groups showed a sensitivity of about 60%, whereas specificity ranged from 65% to 50%. The combined use of the terms correlated significantly with responses regarding indication for legal detention for psychiatrists and nursing staff. CONCLUSION: In identifying a patient as 'psychotic' a broad concept of impaired reality testing was widely used particularly in cases with legal issues. Psychotic symptoms, however, were identified with high sensitivity and specificity.

Linking integrated water resources management and integrated coastal zone management.

Some of the world's most valuable aquatic ecosystems such as deltas, lagoons and estuaries are located in the coastal zone. However, the coastal zone and its aquatic ecosystems are in many places under environmental stress from human activities. About 50% of the human population lives within 200 km of the coastline, and the population density is increasing every day. In addition, the majority of urban centres are located in the coastal zone. It is commonly known that there are important linkages between the activities in the upstream river basins and the environment conditions in the downstream coastal zones. Changes in river flows, e.g. caused by irrigation, hydropower and water supply, have changed salinity in estuaries and lagoons. Land use changes, such as intensified agricultural activities and urban and industrial development, cause increasing loads of nutrients and a variety of chemicals resulting in considerable adverse impacts in the coastal zones. It is recognised that the solution to such problems calls for an integrated approach. Therefore, the terms Integrated Water Resources Management (IWRM) and Integrated Coastal Zone Management (ICZM) are increasingly in focus on the international agenda. Unfortunately, the concepts of IWRM and ICZM are mostly being developed independently from each other by separate management bodies using their own individual approaches and tools. The present paper describes how modelling tools can be used to link IWRM and ICZM. It draws a line from the traditional sectoral use of models for the Istanbul Master Planning and assessment of the water quality and ecological impact in the Bosphorus Strait and the Black Sea 10 years ago, to the most recent use of models in a Water Framework Directive (WFD) context for one of the selected Pilot River Basins in Denmark used for testing of the WFD Guidance Documents.

First European interlaboratory study of the analysis of benzoxazinone derivatives in plants by liquid chromatography.

Six laboratories from four different countries participated in the first European interlaboratory comparison exercise within the framework of the "Fate and toxicity of allelochemicals (natural plant toxins) in relation to environment and consumer" (FATEALLCHEM) European Union Project. The study, organized between November 2002 and March 2003, involved the analyses of seven benzoxazinone derivatives in two standard solutions and one purified extract of root material. Results are reported from the first phase of the study that examined the variability associated with different detection methods and different laboratories. The analytical strategies were based on liquid chromatography (LC) with diode array detection, LC coupled to mass spectrometry (MS) and LC coupled to tandem MS. When data from all laboratories were pooled, the relative standard deviation values ranged from 2 to 14% for the determination of target compounds in standard solutions, and between 19 and 47% for the analysis in root material. Comparison of the three detection techniques leads to the conclusion that MS approaches are the most accurate and precise techniques for the determination of benzoxazinone derivatives at ng/microL level in plant material.

Purification of triolein for use in semipermeable membrane devices (SPMDs).

Analyses of triolein-containing semipermeable membrane devices (SPMDs) have sometimes been impeded by interferences caused by impurities endemic to triolein that codialyze with the analytes. Oleic acid and methyl oleate have been the most troublesome of these impurities because of their relatively high concentrations in triolein and because significant residues of both can persist even after size exclusion chromatographic (SEC) fractionation. These residues have also been blamed for false-positive signals during bioindicator testing of SPMD dialysates. To prevent these problems, a simple, cost-effective procedure was developed for purifying triolein destined for use in SPMDs: the bulk triolein is repeatedly (6x) partitioned against methanol. Tests of the procedure show that 14C-oleic acid is completely removed from the triolein. After SEC fractionation, dialysates of standard-size SPMDs made with the purified triolein contain less than 5 microg of methyl oleate as compared to sometimes more than 500 microg for dialysates (also after SEC) of SPMDs made with unpurified triolein. Gas chromatographic analyses with flame ionization and electron capture detection show that the purification treatment also greatly reduces the number and size of peaks caused by unidentified contaminants in the triolein. Microtox basic assay of dialysates of SPMDs shows that those made with the purified triolein have lower acute toxicities than dialysates of SPMDs made with unpurified triolein. Yeast estrogen screen (YES) testing of SPMDs fabricated with unpurified and purified triolein demonstrates that the purification process removes all background estrogenic activity.

Environmental properties and effects of nonionic surfactant adjuvants in pesticides: a review.

Little is known about the environmental fate of adjuvants after application on the agricultural land. Adjuvants constitute a broad range of substances, of which solvents and surfactants are the major types. Nonionic surfactants such as alcohol ethoxylates (AEOs) and alkylamine ethoxylates (ANEOs) are typically examples of pesticide adjuvants. In view of their chemical structure this paper outlines present knowledge on occurrence, fate and effect on the aquatic and terrestrial environment of the two adjuvants: AEOs and ANEOs. Both AEOs and ANEOs are used as technical mixtures. This implies that they are not one single compound but a whole range of compounds present in different ratios. Structurally both groups of substances have a mutual core with side chains of varying lengths. Each of these compounds besides having the overall ability to distribute between different phases also possesses some single compound behaviour. This is reflected in the parameters describing the fate e.g. distribution coefficient, leaching, run-off, adsorption to soil, degradation and effects of these substances. The adsorption behaviour of ANEOs in contrast to AEOs is particularly variable and matrix dependent due to the ability of the compound to ionise at environmentally relevant pH. Probably because the compounds exceeds high soil adsorption and are easily degradable which is reflected in the low environmental concentrations generally found in monitoring studies. The compounds generally possess low potency to both terrestrial and aquatic organisms. The major environmental problem related to these compounds is the ability to enhance the mobility of other pollutants in the soil column.

Analysis of polar pesticides in rainwater in Denmark by liquid chromatography-tandem mass spectrometry.

A new LC-MS-MS method for analysis of rainwater has been developed and validated for 53 pesticides, degradation products of pesticides and selected nitrophenols. The method was used to monitor the concentration of pesticides in rainwater at one location near Roskilde, Denmark from February 2000 to August 2000. Sampling was done in periods of up to 4 weeks using a cooled wet-only sampler. Water samples were extracted by solid-phase extraction on Oasis HLB columns. The analysis of the extracts was performed by LC-MS-MS with electrospray ionization. All samples were analysed in negative and in positive ionization mode, respectively for acidic and neutral compounds. All analyses were done in the selected reaction monitoring mode in order to obtain a better signal-to-noise ratio. The method has been validated for the following parameters: recovery, detection limit, uncertainty and linearity. Atrazine, terbuthylazine, isoproturon, mechlorprop and (2-methyl-4-chlorophenoxy)acetic acid were measured at concentrations above 0.100 microg/l, mainly during the period of agricultural use. Nitrophenols were measured at high concentrations all year with peaks in the cold season (February-March).

Fate and effects of esfenvalerate in agricultural ponds.

The fate of esfenvalerate was investigated by sampling and chemical analysis after spraying of an artificial pond (25 g a.i./ha) and in the laboratory with [14C]esfenvalerate by trapping of 14CO2 and fractionation of the sediment. The effects were investigated on pelagic communities in enclosures in a natural lake and in the laboratory on surface (Cymatia coleoptrata) and sediment (Chironomus riparius) insects. The latter were used in sediment-plus-water and in water-only tests, measuring effects on emergence and mortality. The measurements in the artificial pond indicated exposure concentrations in the surface microlayer, water column, and sediment of 0.4 microgram/L, 0.05 microgram/L, and 9 micrograms/kg dry weight, respectively, two weeks after application. The degradation studies showed a limited mineralization (26.5%) of [chorophenyl-14C]esfenvalerate during 112 d. Part of the substance was transformed to water-soluble compounds (18.1%) or compounds attached to fulvic acids (26.2%), humic acids (14.2%), or nonextractable sediment constituents (8.8%). The formulated product Sumi-Alpha 5 FW caused 100% mortality to Cymatia coleoptrata after surface application of 0.13 g a.i/ha. Effects on zooplankton were recorded at 0.005 microgram/L of esfenvalerate. The 96-h median lethal concentration for first-instar larvae of Chironomus riparius was 0.13 microgram/L, whereas the delayed emergence lowest-observed-effect concentration was 0.8 microgram/L.

The influence on partial order ranking from input parameter uncertainty. Definition of a robustness parameter.

The method of partial order ranking has been used within the environmental area for a variety of purposes as an attractive way of handling complex information. However, the environmental data are often associated with a significant degree of uncertainty. In this investigation the general nature of the influence from data uncertainty on the partial order ranking is analyzed. A Monte Carlo type analysis is performed in which a series of randomly formed data are used to test the influence of data uncertainty. The partial order ranking is interpreted, where the results are transferred to a one-dimensional ranking scale taking into account that not all elements are ranked with the same certainty. A simple general robustness parameter (E) in form of the expected number of comparisons for each ranking element is defined and correlated to the uncertainty analysis results. A simple equation relates E to the number of elements and the number of parameters, respectively. The magnitude of the ranking uncertainty is shown to increase rapidly when the E value decreases below 4-5 comparisons per element. When the E value exceeds 5 the ranking uncertainty becomes nearly constant and independent on the actual E value.

Can manipulation of a pelvic tumour influence the serum level of cancer antigen 125 and cancer-associated serum antigen?

Cancer antigen 125 (CA 125) and cancer-associated serum antigen (CASA) were measured in 24 women with pelvic masses before and after a gynaecological examination and ultrasonography. CA 125 decreased median 16% after manipulation (P < 0.0001) and CASA decreased median 8% (P = 0.0077). The decline was found in patients with benign tumours as well as in patients with malignant tumours.

Elevated serum insulin-like growth factor-binding protein 2 (IGFBP-2) and decreased IGFBP-3 in epithelial ovarian cancer: correlation with cancer antigen 125 and tumor-associated trypsin inhibitor.

Insulin-like growth factors (IGFs) and IGF-binding proteins (IGFBPs) recently have been shown to play a physiological role in the female genital system, including the ovarian follicular system. However, little is known about the role of the IGF system in malignant ovarian disease. To assess possible mutual correlations between alterations in circulating IGFBP profiles and tumuor markers in patients with epithelial ovarian cancer, we performed an RIA for IGFBP-2 and IGFBP-3 and a Western ligand blotting (WLB) in serum samples from 20 patients with epithelial ovarian cancer, 10 patients with benign ovarian tumors, and 8 healthy age-matched controls. The epithelial ovarian cancer group had a mean IGFBP-2 level that was 253% (RIA) and 105% (WLB) above that of controls. IGFBP-2 even correlated positively with the highly sensitive serum tumor marker, cancer antigen 125 (CA 125) (r = 0.71, P < 0.001) but not with the less sensitive tumor-associated trypsin inhibitor. In contrast, serum IGFBP-3 (by RIA and WLB) was decreased in patients with ovarian cancer, and IGFBP-3 proteolytic activity was detectable in some of the patients. Neither IGFBP-3 nor IGFBP-3 proteolytic activity correlated with CA 125; but the former correlated inversely, and the latter positively, with tumor-associated trypsin inhibitor. In conclusion, IGFBP-2 levels are high in serum of epithelial ovarian cancer patients, and the increment in serum IGFBP-2 correlates positively with CA 125. Alterations in serum IGFBP-2 levels may therefore, serve as a potential additional marker for ovarian cancer.

Epidemiology of childhood injuries in Reykjavík 1974-1991.

OBJECTIVE: To determine and analyse the incidence of childhood injuries in Reykjavík 1974-1991. DESIGN: Descriptive, retrospective study. SETTING: Reykjavík City district with a mean number of 88700 inhabitants, of which 23.4% were children under 15 years of age. SUBJECTS: All children 0-14 years old who came to the emergency department at Reykjavík City Hospital because of an injury. MAIN OUTCOME MEASURES: Number of injured children per 1000 children per year. RESULTS: 111726 cases were studied. The total incidence of injuries increased from 275 per 1000 children per year in 1974-76 to 327 in 1980-82, but it then decreased to 275 in 1989-91. The injury incidence for 0-4 years old decreased from 353 in 1980-82 to 259 in 1989-91. The injury incidence for children 5-9 years old was 249 in 1989-91. The injury incidence for children 10-14 years old increased from 235 in 1974-76 to 336 in 1980-82, and in 1989-91 it was 321. The incidence of hospital admissions was 7.6 per 1000 children per year, or 2.6%. The child accident mortality rate in Reykjavík from 1987-1991 was 6.5 per 100000 children per year. CONCLUSION: Childhood injuries in Reykjavík are far too many, and a major effort is needed to reduce their number.

Flow cytometric DNA analyses of 105 fresh hydatidiform moles, with correlations to prognosis.

Cellular DNA contents of consecutive hydatidiform moles were analysed by flow cytometry of unfixed samples, freed of maternal tissue and treated with detergent and trypsin, using two external controls. DNA-diploidy was found in 62 moles, DNA-triploidy in 42 and DNA-tetraploidy in one. Two non-molar placentas and two invasive moles were found to be DNA-diploid. In 28 of 42 DNA-triploid moles, trophoblastic hyperplasia was not noted, making the discrimination between vesicular abortions with or without trophoblastic hyperplasia unwarranted on genetic grounds. A good fit was obtained to a distribution with one G0-1 peak in 49 cases, whereas 60 cases showed two peaks. Technical artifacts, created by flow cytometry, were excluded. Differences in the nuclear accessibility for the dye and degradation of DNA are unlikely causes of this heterogeneity. The existence, in vivo, of two or more cell populations with different DNA contents is a reasonable explanation. The criteria for persistent trophoblastic disease were standardised. Eight cases of persistent trophoblastic disease were observed among the 62 DNA-diploid moles (13%); no case was observed after DNA-triploid or DNA-tetraploid moles. Combining these data, with those of other studies where ploidy was determined using optimal techniques [10,13], allows the calculation of 95%-confidence-limits for the risk of persistent trophoblastic disease after a triploid mole to 0-2.7%.