Acute aquatic toxicity of arsenic-based chemical warfare agents to Daphnia magna.

Sea dumping of chemical warfare (CW) took place worldwide during the 20th century. Submerged CW included metal bombs and casings that have been exposed for 50-100 years of corrosion and are now known to be leaking. Therefore, the arsenic-based chemical warfare agents (CWAs), pose a potential threat to the marine ecosystems. The aim of this research was to support a need for real-data measurements for accurate risk assessments and categorization of threats originating from submerged CWAs. This has been achieved by providing a broad insight into arsenic-based CWAs acute toxicity in aquatic ecosystems. Standard tests were performed to provide a solid foundation for acute aquatic toxicity threshold estimations of CWA: Lewisite, Adamsite, Clark I, phenyldichloroarsine (PDCA), CWA-related compounds: TPA, arsenic trichloride and four arsenic-based CWA degradation products. Despite their low solubility, during the 48 h exposure, all CWA caused highly negative effects on Daphnia magna. PDCA was very toxic with 48 h D. magna LC50 at 0.36 µg × L-1 and Lewisite with EC50 at 3.2 µg × L-1. Concentrations at which no immobilization effects were observed were slightly above the analytical Limits of Detection (LOD) and Quantification (LOQ). More water-soluble CWA degradation products showed no effects at concentrations up to 100 mg × L-1.

Acute aquatic toxicity of sulfur mustard and its degradation products to Daphnia magna.

Sulphur mustard (HD) was the most widely produced chemical warfare agent (CWA) in the history of chemical warfare (CW). Simultaneously, the loads of HD account as by far the largest fraction of the sea-dumped CW. Nowadays its presence in the marine ecosystems recognized as a serious threat for marine users and maritime industries. Although, during over a decade of research much has been done to assess the environmental threats linked with underwater chemical munitions. There are, however, essential gaps in scientific knowledge including scarce information about the aquatic toxicity thresholds of HD and its degradation products. Standardized biotests were performed according to the Organisation for Economic Co-operation and Development (OECD) Test No. 202: Daphnia sp. Acute Immobilisation Test guidelines. Obtained results provide a solid foundation for comparison and categorisation of threats of HD and its degradation products. With the D. magna LC50 aquatic acute toxicity threshold at as low as 224 ± 12 µg × L-1, 1,2,5-trithiepane is very toxic, being one of the most toxic CWA degradation products that have been investigated up to date. It exhibits stronger effects than 1,4,5-oxadithiepane and diluted HD that turn out to be toxic. In total, the toxicity of 7 compounds has been estimated. Whenever possible, toxicity thresholds were compared with previously existing data originating from different biotests and mathematical modelling.

Analysis of samples of explosives excavated from the Baltic Sea floor.

After World War II, conventional and chemical ammunition containing mainly secondary and primary explosives was dumped in the sea. Explosives have medium toxicity to aquatic organisms, earthworms and indigenous soil microorganisms. Therefore, environmental monitoring is required, especially for dumped munitions. The main aspect of this work was to analyse the samples of lumps and sediments taken from the Baltic seabed. These samples were potentially explosives. The main goal of the study was to identify the type and composition of studied materials. In order to determine the chemical composition of samples of explosives, we used as follows: GC-MS/MS, LC-HRMS and NMR. Additionally, to determine the energetic properties we performed microcalorimetric-thermogravimetric analysis. Based on the obtained results, the composition of this explosive was TNT (41%), RDX (53%), aluminium powder (5%), and degradation products (below 1%). The resulting composition indicates that the analysed material can be classified in the "torpex" family, widely used during World War II. Regarding the results of the microcalorimetric analysis, we can conclude that excavated fragments of explosives are in very good condition and they still can detonate after being initiated. Therefore, there is a threat that they could be used for criminal or terrorist purposes.

Bacterial benthic community composition in the Baltic Sea in selected chemical and conventional weapons dump sites affected by munition corrosion.

Microflora of marine waters and sediments play a significant role not only in the course of natural changes and circulation of elements in this environment, but can also be a decisive factor during erosion processes of various submerged objects or structures such as wrecks, sunken objects, pipelines, etc. The bacteria which have a significant influence on corrosion processes include aerobic and anaerobic sulfur bacteria as well as iron bacteria. Particular importance is attributed to sulfide reducing bacteria (SRB) which occur in waters, bottom sediments, creating biofilms on metal surface, and may start a process known as microbial induced corrosion (MIC). The occurrence of these bacteria and their populations indicates potential and intensification of corrosion processes. The aim of the study was to determine the number of microorganisms from various groups in the Baltic Sea sediments, especially those that are active in biological corrosion processes. This data can be used for a study comprehensive of corrosive processes in the marine environment, and as a result, to carry out a real assessment of the risks arising from the release of toxic substances into the environment from conventional and chemical weapons lying on the bottom caused by progressing corrosive processes, including biological corrosion. The article presents the results of research on the presence and accounts of microorganisms in bottom sediment samples taken from the dump sites of chemical and conventional ammunition in the Baltic Sea. Particular attention was paid to halophilic and halotolerant bacteria due to their significant contribution to both corrosion and decomposition processes of CWA and explosives, particularly in the saltwater environment. There were high and quite similar numbers of mesophilic, psychrophilic and halophilic bacteria in the studied samples, while significantly smaller numbers of anaerobic bacteria. The amount of mesophilic bacteria ranges from 6.42*103 to 2.85*107, on average 4.5*106 in 1 g DM, psychrophilic from 5.73*103 in1g DM to 4.11*107 in 1 g DM, on average 6.44*106 in 1 g DM, whereas for halophylic from 4.09*102 to 5.60*107, on average 5.83*106 in1g DM. The numbers of fungi were at a much lower level and ranged from 4.65*101 to 8.08*102, on average 2.63*102 in 1 g DM. mesophilic fungi and from 0 to 1.60*103, on average 3.58*102 in 1 g DM for psychrophilic fungi. The presence of sulfide reducing bacteria (SRB) was also detected in large populations, especially when they were isolated by means of the medium prepared with seawater (from 9.72 to 5.36*102, on average 2.52*102 in 1 g DM), which indicates their adaptation to the saline environment and promotes of biological anaerobic processes, including corrosive processes. No significant amounts of iron bacteria were found, probably due to the small amount of oxygen in the sampling area. The small number of iron bacteria indicates that primarily anaerobic sulfide reducing bacteria (SRB) have the major part in the microbial corrosion phenomena.

Sea-dumped ammunition as a possible source of mercury to the Baltic Sea sediments.

After World War II, as a move toward Germany demilitarization, up to 385,000 t of munitions were sunk in the Baltic Sea. Munition containing various harmful substances, including chemical warfare agents (CWA) and explosives, that can affect marine biota were dumped on the seafloor. Some of those objects contained mercury, either as elemental mercury or mercury compounds (e.g., mercury fulminate, a common explosive primer), and thus could act as a specific local source of mercury in the dumping areas. Unfortunately, there is a lack of information on how dumped munitions impact the mercury concentrations in the Baltic Sea sediments. This report aims to answer the question how much sedimentary mercury in the dumping areas originates from munitions and to determine to what extent the mercury present in those areas originates from mercury fulminate. Concentrations of total sedimentary mercury- HgTOT in samples collected from conventional (Kolberger Heide) and chemical (Bornholm Deep) munitions dumping sites are characterized by high variability. However, an increase in HgTOT concentrations was observed with a decreasing distance to particular munition objects at both study sites. Moreover, mercury speciation in sediments from Kolberger Heide proves that the mercury there can be traced back directly to mercury fulminate. Results of our study confirm that munitions dumpsites are a local point sources of mercury. Due to the ecosystem constrains, varying transport modes and pathways, and both unknown and varying decomposition rates, these sea-bed mercury concentrations are hard to evaluate quantitatively. Therefore we recommend that further detailed studies should be conducted to assess sedimentary mercury provenience in munitions dumpsites more accurately.

Overweight and obesity versus concentrations of VEGF-A, sVEGFR-1, and sVEGFR-2 in plasma of patients with lower limb chronic ischemia.

OBJECTIVE: Being overweight or obese comprises a significant risk factor for atherosclerosis. Fat tissue also generates factors stimulating angiogenesis, the process by which new blood vessels form. The purpose of this paper is to assess concentrations of the vascular endothelial growth factor A (VEGF-A) and its soluble type-1 and type-2 receptors (sVEGFR-1 and sVEGFR-2) in plasma of patients with peripheral arterial disease (PAD) depending on the level of nutrition according to body mass index (BMI). METHODS: The study group included patients suffering from symptomatic PAD (n=46) in Fontaine classes IIa-IV without any history of neoplastic disease and who have a normal BMI (n=15), are overweight (n=21) or are obese (n=10). The control group (n=30) consisted of healthy non-smoking volunteers who were neither overweight nor obese. Venous blood plasma samples were collected from both groups at rest in the morning to determine plasma concentrations of VEGF-A, sVEGFR-1, and sVEGFR-2 using the enzyme-linked immunosorbent assay (ELISA) method. RESULTS: The group of patients with PAD co-existent with being overweight or obese tended to have higher mean concentration levels of VEGF-A and sVEGFR-2 when compared with patients suffering from PAD with normal BMI. A statistically significant positive correlation was obtained between BMI and average plasma concentrations of sVEGFR-2 (R=0.37, P=0.0103). However, no significant correlation was noticed between BMI and VEGF-A or sVEGFR-1 concentrations. CONCLUSIONS: A positive correlation determined between the level of antiangiogenic factor and BMI value may be indicative of the linearly growing prevalence of some antiangiogenic factors in patients with metabolic disorders, which may be one of numerous factors contributing to incomplete efficiency of collateral circulation development in patients with PAD.

Impact of type 2 diabetes on the plasma levels of vascular endothelial growth factor and its soluble receptors type 1 and type 2 in patients with peripheral arterial disease.

OBJECTIVE: Type 2 diabetes coexistent with lower extremity artery disease (peripheral arterial disease (PAD)) can be observed in numerous patients. The mechanism compensating for ischemia and contributing to healing is angiogenesis-the process of forming new blood vessels. The purpose of this study was to assess the likely impact of type 2 diabetes on the plasma levels of proangiogenic factor (vascular endothelial growth factor A (VEGF-A)) and angiogenesis inhibitors (soluble VEGF receptors type 1 and type 2 (sVEGFR-1 and sVEGFR-2)) in patients with PAD. METHODS: Among 46 patients with PAD under pharmacological therapy (non-invasive), we identified, based on medical history, a subgroup with coexistent type 2 diabetes (PAD-DM2+, n=15) and without diabetes (PAD-DM2-, n=31). The control group consisted of 30 healthy subjects. Plasma levels of VEGF-A, sVEGFR-1, and sVEGFR-2 were measured using the enzyme-linked immunosorbent assay (ELISA) method. RESULTS: The subgroups of PAD-DM2+ and PAD-DM2- revealed significantly higher concentrations of VEGF-A (P=0.000 007 and P=0.000 000 1, respectively) and significantly lower sVEGFR-2 levels (P=0.02 and P=0.000 01, respectively), when compared with the control group. Patients with PAD and coexistent diabetes tended to have a lower level of VEGF-A and higher levels of sVEGFR-1 and sVEGFR-2 comparable with non-diabetic patients. CONCLUSIONS: The coexistence of type 2 diabetes and PAD is demonstrated by a tendency to a lower plasma level of proangiogenic factor (VEGF-A) and higher levels of angiogenesis inhibitors (sVEGFR-1 and sVEGFR-2) at the same time. Regardless of the coexistence of type 2 diabetes, hypoxia appears to be a crucial factor stimulating the processes of angiogenesis in PAD patients comparable with healthy individuals, whereas hyperglycemia may have a negative impact on angiogenesis in lower limbs.

Improvement in health-related quality of life after therapy with omeprazole in patients with coronary artery disease and recurrent angina-like chest pain. A double-blind, placebo-controlled trial of the SF-36 survey.

BACKGROUND: Many patients with coronary artery disease (CAD) have overlapping gastroenterological causes of recurrent chest pain, mainly due to gastroesophageal reflux (GER) and aspirin-induced gastrointestinal tract damage. These symptoms can be alleviated by proton pump inhibitors (PPIs). The study addressed whether omeprazole treatment also affects general health-related quality of life (HRQL) in patients with CAD. STUDY: 48 patients with more than 50% narrowing of the coronary arteries on angiography without clinically overt gastrointestinal symptoms were studied. In a double-blind, placebo-controlled, cross-over study design, patients were randomized to take omeprazole 20 mg bid or a placebo for two weeks, and then crossed over to the other study arm. The SF-36 questionnaire was completed before treatment and again after two weeks of therapy. RESULTS: Patients treated with omeprazole in comparison to the subjects taking the placebo had significantly greater values for the SF-36 survey (which relates to both physical and mental health), as well as for bodily pain, general health perception, and physical health. In comparison to the baseline values, therapy with omeprazole led to a significant increase in the three summarized health components: total SF-36; physical and mental health; and in the following detailed health concept scores: physical functioning, limitations due to physical health problems, bodily pain and emotional well-being. CONCLUSIONS: A double dose of omeprazole improved the general HRQL in patients with CAD without severe gastrointestinal symptoms more effectively than the placebo.

Plutonium bioaccumulation in seabirds.

The aim of the paper was plutonium (²³8Pu and ²³9⁺²4°Pu) determination in seabirds, permanently or temporarily living in northern Poland at the Baltic Sea coast. Together 11 marine birds species were examined: 3 species permanently residing in the southern Baltic, 4 species of wintering birds and 3 species of migrating birds. The obtained results indicated plutonium is non-uniformly distributed in organs and tissues of analyzed seabirds. The highest plutonium content was found in the digestion organs and feathers, the smallest in skin and muscles. The plutonium concentration was lower in analyzed species which feed on fish and much higher in herbivorous species. The main source of plutonium in analyzed marine birds was global atmospheric fallout.

Treatment with double dose of omeprazole increases ß-endorphin plasma level in patients with coronary artery disease.

INTRODUCTION: The proton pump inhibitor empirical trial, besides the analysis of symptoms, is the main method in the diagnosis of gastro-oesophageal reflux disease-related chest pain. ß-Endorphin acts as an endogenous analgesia system. The aim of the study was verify whether ß-endorphin plasma level is affected by omeprazole administration and influences the severity of anginal symptoms and outcome of the "omeprazole test" in patients with coronary artery disease (CAD) and chest pain of suspected non-cardiac origin. MATERIAL AND METHODS: Omeprazole was administered to 48 patients with CAD in a randomized, placebo-controlled, crossover study design. At the beginning of the study, and again after the 14-day omeprazole and placebo treatment, the ß-endorphin plasma concentration was determined. RESULTS: The level of plasma ß-endorphin after the administration of omeprazole was significantly greater than at the start of the study and following the placebo. Responders to omeprazole had an average lower ß-endorphin plasma concentration than subjects who failed to respond to this therapy. Subjects with symptoms in class III (according to the Canadian Cardiovascular Society classification) after omeprazole administration had a greater ß-endorphin plasma level than subjects in class II for anginal symptom severity. CONCLUSIONS: Fourteen-day therapy with a double omeprazole dose significantly increases the ß-endorphin plasma concentration in patients with CAD. Circulating ß-endorphin does not seem to be involved in the mechanism for the "omeprazole test" outcome, although an individually different effect on pain threshold cannot be excluded.

The effect of double dose of omeprazole on the course of angina pectoris and treadmill stress test in patients with coronary artery disease--a randomised, double-blind, placebo controlled, crossover trial.

BACKGROUND: Gastroesophageal reflux (GER) and coronary artery disease (CAD) frequently overlap, making the proper diagnosis of chest pain more difficult. GER symptoms may mistake anginal chest pain, and oesophageal acidification may induce myocardial ischaemia both in the rest and in the effort. Increase of oesophageal pH should prevent these conditions. AIM: To estimate the effect of double omeprazole dose on the course of angina pectoris and treadmill stress test in patients with coronary artery disease (CAD), using double-blind, crossover randomised, placebo-controlled study design. METHODS: We studied 48 patients with angina pectoris symptoms and significant narrowing of coronary vessels in angiography. After baseline examination and treadmill stress test all subjects were randomised to treat either with omeprazole (20 mg b.i.d.) or placebo for 14 days, using a double-blind, crossover placebo controlled design. RESULTS: Seventeen (35%) subjects reported more than by half decrease in symptoms severity after omeprazole and 6 (12%) after placebo (p=0,01). Omeprazole significantly decreased the number of chest pain episodes and number of nitroglycerin doses taken in the second week of both study phases, as well as the percentage of subjects with significant decrease of ST interval during the stress test (64% vs. 73%, p<0,05). However majority of other stress test parameters (i.e. test duration, DUKE index) have improved both after omeprazole and placebo administration (by 9-38%). CONCLUSION: Double dose of omeprazole significantly decreased symptoms severity in 35% of patients with CAD, as well as frequency of some electrocardiographic signs of myocardial ischaemia during stress test.

[The effect of hypolipemic therapy with diet and simvastatin on the course of angina pectoris and the results of exercise stress test in patients with coronary artery disease]. / Wplyw leczenia hipolipemizujaego dieta i simwastatyn na przebieg dusznicy bolesnej i wyniki elektrokardiograficznej próby wysilkowej u pacjentów z choroba niedokrwienna serca.

UNLABELLED: Statins are the multi-directorial acting drugs in atherosclerosis prevention, which decrease the overall and cardiovascular mortality. The aim of this study was to estimate the effect of six-month long hypolipemic therapy with diet and 20 mg of simvastatin on clinical intensity of angina pectoris and the course of exercise stress test. PATIENTS AND METHODS: We studied 44 patients with typical anginal chest pain. In all blood sampling and treadmill stress test were made, and next in all hypolipemic diet and simvastatin 20 mg were recommended. After four weeks and six months of treatment clinical assessment and exercise test were made. RESULTS: After four weeks and six month long observation period the decrease of total and LDL cholesterol, triglycerides and fibrinogen were found. Moreover, we have observed the improvement in frequency of anginal symptoms, their intensity in CCS classification and number of nitroglycerin tablets taken per week. The course of exercise test was also ameliorated: the percentage of patients, in whom stress test was finished because of chest pain was decreased, time of chest pain duration after exercise cessation was shorter, the percentage of patients with significant ST interval depression diminished, maximal ST interval depression as well as the time of significant ST interval depression duration also decreased. Although improvement in values of mentioned parameters, after six months long therapy with simvastatin the percentage of patients with Duke's treadmill score value showing intermediate cardiovascular risk (between -10 and +4) increased. In conclusion, therapy with hypolipemic diet and simvastatin already after four weeks decreased plasma lipids and fibrinogen levels and improved the course of angina pectoris and exercise stress test, what suggested its effectiveness not only as the treatment improving atherosclerosis risk factors, but also with prompt and clinical important effect ameliorating the handicapped coronary reserve.

Suppression of gastric acid production may improve the course of angina pectoris and the results of treadmill stress test in patients with coronary artery disease.

BACKGROUND: Coronary artery disease (CAD) and gastro-esophageal reflux disease (GERD) often coexist in the same patients. The aim of this study was to estimate the effects of gastric acid output suppression with rabeprazole on course of angina pectoris and results of the treadmill stress test in patients with CAD. MATERIAL/METHODS: We studied 34 patients with stable angina pectoris. In all subjects a medical history, a physical examination, and a stress test were performed at the beginning of the study and after two weeks of add-on rabeprazole therapy (20 mg b.i.d.). RESULTS: Rabeprazole therapy significantly improved the outcome of the stress test in 27 patients (79%), prolonging mean stress exercise time (449+/-147 vs. 489+/-156s, p=0.027) and exercise time, leading to a maximum ST interval depression (360+/-167 vs. 467+/-148s, p=0.001), and also decreasing ST interval depression delta (1.9+/-1.1 vs. 1.5+/-0.9; p=0.013). CONCLUSIONS: In 79% of our study subjects, rabeprazole improved stress test results in CAD patients, which implies that at least some of their symptoms were related to GERD. A proton pump inhibitor exerted a favorable effect on the frequency of angina-like chest pain and the results of the treadmill stress test.

The effect of eight weeks of rabeprazole therapy on nitric oxide plasma level and esophageal pH and motility and motility nitric oxide plasma level in patients with erosive esophagitis.

BACKGROUND: Esophageal clearance, an important pathogenetic factor in gastroesophageal reflux disease, depends mainly on motility. Motility disturbances can be secondary to gastric output reflux. Nitric oxide influences esophageal motility. The aim of this study was to determine the effect of eight weeks of gastric acid secretion suppression with rabeprazole (20 mg/day) on esophageal motility. MATERIAL/METHODS: 20 patients with erosive esophagitis were studied. At study start and two weeks after the end of therapy, we recorded the results of interview, endoscopy, gastric and esophageal mucosa biopsy, 24-h esophageal pH-metry and manometry, and NO metabolites plasma concentration, determined spectrophotometrically (OXIS). RESULTS: All patients reported improvement and remained free of symptoms two weeks later. In 60% of cases, improvement of esophageal mucosa appearance was observed in endoscopic and histological examination. In follow-up we found a significantly smaller number of acid gastrooesophageal refluxes (p<0.05), reduced DeMeester score for pH range >7 (p<0.05), and greater % of time within the esophageal pH range 6-7 (p<0.05). Other esophageal pH-metry and 24-h manometry parameters did not change significantly. NO metabolites plasma concentration increased significantly (p=0.039). CONCLUSIONS: Clinical improvement after eight weeks of therapy with rabeprazole was connected with endoscopic changes only in 60% of our patients. Rabeprazole therapy did not influence esophageal motility, despite increased plasma levels of NO metabolites. Patients with erosive esophagitis need maintenance therapy, since as soon as two weeks after the end of treatment the % of monitoring time with esophageal pH<4 was similar to study start.