Fate of pharmaceutical residue in two Romanian rivers receiving treated water: Occurrence, distribution and risk assessment.

This study presents the first set of data on the removal of proton pump inhibitors (PPIs) and histamine H2 receptor antagonists (HRAs) and their transformation products in two Romanian wastewater treatment plants (WWTPs), as well as the impact of these organic pollutants on freshwater receiving effluents. The research investigated eight target pharmaceuticals and three metabolites using a newly developed and validated Liquid Chromatography - Mass Spectrometry (LC-MS/MS) method. The combined determination had a range of quantification limits varying from 0.13 ng/L to 0.18 ng/L for surface water and from 0.28 ng/L to 0.43 ng/L for wastewater. All analytes except cimetidine and 5-hydroxy-omeprazole were identified in water samples. The study found similar overall removal efficiencies for both WWTPs (43.2 % for Galati and 51.7 % for Ramnicu-Valcea). The research also showed that ranitidine and omeprazole could pose a low to high ecological risk to aquatic organisms. The findings suggest that the treatment stages used in the two Romanian WWTPs are insufficient to remove the target analytes completely, leading to environmental risks associated with the occurrence of pharmaceutical compounds in effluents and freshwater.

Occurrence and distribution of azole antifungal agents in eight urban Romanian waste water treatment plants.

Azole compounds are utilized to combat fungal infections in plants to protect them and also used for treating mycosis in humans. The LC-MS/MS method is a technique that combines liquid chromatography with tandem mass spectrometry for analysis of twelve azole compounds from wastewater (influent, effluent) and sewage sludge. The compounds were isolated from waste water using automatic extraction in the solid phase. Sludge samples were dried by lyophilization, after which they were subjected to ultrasound extraction with methanol. The quantification limits ranged from 0.3 ng/L (clotrimazole-CLO and prochloraz-PRO) to 1.5 ng/L (tetraconazole-TEB and penconazole-PEN), for wastewater samples and for sewage sludge, the LOQs ranged from 0.1 ng/g to 0.6 ng/g. High concentrations of climbazole-CLI (207-391 ng/L), tebuconazole (92-424 ng/L), and clotrimazole (6.9-93-ng/L) were observed in influent samples of the 8 urban wastewater treatment plants, followed by fluconazole (49.3-76.8 ng/L), and prochloraz (7.3-72 ng/L). The ∑Azoles had a maximum of 676 ng/L in the Galati effluent, followed by the Bucharest station 357 ng/L, and 345 ng/L in the Braila effluent. The highest value of the daily mass loading (input) level was observed for climbazole, 265 mg/day/1000 in Iasi station, followed by tebuconazole, 238 mg/day/1000 people in the Bucharest station, and 203 mg/day/1000 people for climbazole in the Targoviste station. The daily mass emission presented values between 0.7 and 247 mg/day/1000 people. The highest emissions were observed for climbazole, 247 mg/day/1000 people in Braila station; 174 mg/day/1000 people in the Iasi station and 129 mg/day/1000 people in the Bucharest station. The concentrations of climbazole detected in the effluent can present a high risk for the plants Lemna minor and Navicula pelliculosa. Clotrimazole may present a high risk to the plant Desmodesmus subspicatus and to the invertebrate Daphnia magna. PRO may present high risk to the invertebrate Mysidopsis Bahia.

Tissue Bioconcentration Pattern and Biotransformation of Per-Fluorooctanoic Acid (PFOA) in Cyprinus carpio (European Carp)-An Extensive In Vivo Study.

The perfluoroalkyl substances (PFAS) represent a persistent class of synthetic chemicals that spread in the environment as a result of industrialization. Due to their bioaccumulative and endocrine disruption implications, these chemicals can affect food quality and human health, respectively. In the present study, the bioconcentration and biotransformation of perfluorooctanoic acid (PFOA) in common carp (Cyprinus carpio) were evaluated in a biphasic system (exposure and depuration). Carp were continuously exposed, under laboratory conditions, to 10 (Experiment 1) and 100 (Experiment 2) µg/L PFOA for 14 weeks, followed by a wash out period of 3 weeks. Fish organs and tissues were collected at 8, 12, 14 weeks of exposure and at week 17, after the depuration period. The results obtained from the LC-MS/MS analysis showed the presence of PFOA in all studied organs. The highest values of PFOA were identified in the gallbladder (up to 2572 ng/g d.w.) in Experiment 1 and in the gallbladder (up to 18,640 ng/g d.w.) and kidneys (up to 13,581 ng/g d.w.) in Experiment 2. The average BCF varied between 13.4 and 158 L/Kg in Experiment 1 and between 5.97 and 80.3 L/Kg in Experiment 2. Four biotransformation products were identified and quantified in all organs, namely: PFBA, PFPeA, PFHxA, and PFHpA. PFBA was proven to be the dominant biotransformation product, with the highest values being determined after 8 weeks of exposure in the kidney, gallbladder, brain, liver, and gonads in both experiments. Because freshwater fish are an important food resource for the human diet, the present study showed the fishes' capacity to accumulate perfluoroalkyl substances and their metabolites. The study revealed the necessity of monitoring and risk studies of new and modern synthetic chemicals in aquatic resources.

An Initial Survey on Occurrence, Fate, and Environmental Risk Assessment of Organophosphate Flame Retardants in Romanian Waterways.

Organophosphate ester flame retardants (OPFRs) are ubiquitous organic pollutants in the environment and present an important preoccupation due to their potential toxicity to humans and biota. They can be found in various sources, including consumer products, building materials, transportation industry, electronic devices, textiles and clothing, and recycling and waste management. This paper presents the first survey of its kind in Romania, investigating the composition, distribution, possible sources, and environmental risks of OPFRs in five wastewater treatment plants (WWTPs) and the rivers receiving their effluents. Samples from WWTPs and surface waters were collected and subjected to extraction processes to determine the OPFRs using liquid chromatography with mass spectrometric detection. All the target OPFRs were found in all the matrices, with the average concentrations ranging from 0.6 to 1422 ng/L in wastewater, 0.88 to 1851 ng/g dry weight (d.w.) in sewage sludge, and 0.73 to 1036 ng/L in surface waters. The dominant compound in all the cases was tri(2-chloroisopropyl) phosphate (TCPP). This study observed that the wastewater treatment process was inefficient, with removal efficiencies below 50% for all five WWTPs. The environmental risk assessment indicated that almost all the targeted OPFRs pose a low risk, while TDCPP, TCPP, and TMPP could pose a moderate risk to certain aquatic species. These findings provide valuable information for international pollution research and enable the development of pollution control strategies.

Occurrence and Transport of Isothiazolinone-Type Biocides from Commercial Products to Aquatic Environment and Environmental Risk Assessment.

This study investigated the occurrence and transport of four isothiazolinone-type biocides from commercial products to wastewater treatment plants (influents, sludges, and effluents) and to natural emissaries (upstream and downstream the wastewater treatment plants) in Romania. All four biocides were determined in personal care and household products, with the highest concentration of 76.4 µg/L OIT (2-octyl-4-isothiazolin-3-one). For environmental samples, three of the four isothiazolinones were determined, CMI (5-chloro-2-methyl-4-isothiazolin-3-one) being the prominent compound for water samples. The maximum concentration of 84.0 µg/L in influent, 122 µg/L upstream, and 144 µg/L downstream the wastewater treatment plants were obtained for CMI. Unlike water samples, in the sewage sludge samples, OIT proved to be the dominant compound, with concentration up to 5.80 µg/g d.w. The extremely high levels of isothiazolinone determined in different WWTPs from Romania may be due to the COVID-19 pandemic situation, during which a much larger amount of cleaning, hygiene, and personal care products was used. The isothiazolinone-type biocides were readily removed from the influents of the five WWTPs, with the mean removal rate up to 67.5%. The mean mass loading value for the targeted biocides based on influent was 20.4 µg/day/1000 people, while the average environmental emissions were 6.93 µg/day/1000 people for effluents. The results obtained for riverine water combine with statistical analysis showed that the anthropogenic activities are the major contamination sources of the surface waters. Preliminary ecological risk evaluation showed that BIT (1,2-benzisothiazol-3(2H)-one), OIT, and CMI could pose a very high risks to different aquatic species living in the receiving aquatic environments.

Sensitive detection of antidiabetic compounds and one degradation product in wastewater samples by a new SPE-LC-MS/MS method.

As environment emerging contaminants of anthropogenic origin, antidiabetic drugs are present in the range of high ng/L to ng/mL in the influent and the effluent of the waste water treatment plant (WWTP). The metformin compound is the most used hypoglycemic agent in the world. The aim of this study was to develop a new analytic method, based on solid phase extraction followed by liquid chromatography coupled with mass spectrometric detector (SPE-LC-MS/MS), for identification and quantification of 5 antidiabetic compounds (glibenclamide/glyburide, glimepiride, metformin, glipizide, guanyl urea, gliclazide) and one degradation product (guanyl urea). The investigated environmental samples were the influent and the effluent of four urbans WWTP's. By validating of the analytical method, it was obtained low LOQ's (0.2-4.5 ng/L), satisfactory recovery rates (53.6-116.8%), and corresponding performance parameters: inter-day precision (4.9-8.4%) and reproducibility (11.3-14.6%). The concentrations of antidiabetics were as follow in influent and effluent: metformin 76-2041ng/L and 2-206ng/L, gliclazide (14.1-42.4 ng/L, and 3.3-19.1), glipizide (7.5-11.2 ng/L and 6.5-10ng/L), guanyl urea (6.2-7.3 and 8.3-21.3 ng/L). The efficiency of elimination of the antidiabetics in WWTP's was maximum for metformin (67.6-98.5%), followed, by gliclazide (72.9-78.2%). The lowest elimination efficiency was calculated for glipizide (10.7-13.3%). The guanyl urea undergoes a formation process (74.5-84.2%) in effluent, from the metformin contained in influent.

Mg-Zn alloys, most suitable for biomedical applications.

In this review are highlighted the corrosion and biocompatibility of biodegradable Mg alloys for their use in orthopedic applications. It was revealed that mixing with alloying elements, such as Mn and Zn, provides improved corrosion resistance to Mg alloys; this pursuit is built on the fact that Mg and its alloys are degradable through their time in the human body. Furthermore, Mg alloys afford a characteristic profile that is very close or even almost identical to that of human bone. Minimizing the rate of corrosion of Mg is the most adequate method, because a low corrosion rate of an Mg implant involves a decrease in the extent of hydrogen evolution and alkalization, which allow the human body to gradually absorb or consume the corrosion products.

Histological and immunohistochemical study on sentinel lymph node in colorectal cancer - values and limitations.

Colorectal cancer is currently one of the most common malignancies in both men and women. Surgical resection remains the essential element in the local control of the disease but the development of novel diagnostic and therapeutic tools can enhance the results of radical surgery. The indication for adjuvant treatment majorly depends on a correct pathological assessment of the surgical specimen - a correct pTNM staging. For patients diagnosed with stage III disease (characterized by the presence of lymph node metastases), adjuvant chemotherapy increases the survival rate, while in stage II disease, in most cases, the chemotherapy is contraindicated, due to increase morbidity without real benefit. This is why an accurate pN stage becomes essential. It is proven that classic pathological exam sometimes fails to identify lymph node micrometastases or isolate tumor cells, which might explain local or distant relapses in stage II patients. In our study, we evaluated a total of 39 surgical specimens of cTNM stage II patients operated for colon or rectal cancer. In the attempt to enhance the accuracy of pTNM staging we used ex vivo lymph node mapping combined with sentinel node analysis on serial sections in both classical histological and immunohistochemical (IHC) staining. We have demonstrated that the IHC staining on sentinel lymph node can improve the accuracy of pTNM staging, when used as a complementary diagnostic test, by identifying micrometastases and isolated tumor cells.

Squamous esophageal carcinoma and mucinous adenocarcinoma of the colon - an unusual association.

The existence of a simultaneous cancer of the esophagus and colon is a rare situation that recognizes an increased incidence in recent years in the world, probably as a result of the improved measures of diagnosis and treatment, as well as the development of screening programs. The aim of this work is to present a case of synchronous esophageal squamous carcinoma with mucinous adenocarcinoma of the hepatic angle of the colon. The patient was hospitalized to our Surgical Clinic with the thoracic squamous esophageal carcinoma diagnosis. On admission, symptoms were dominated by overall dysphagia, patient showing a weight loss of 10 kg for the last 30 days. Preoperative imaging tests did not revealed regional or distant metastatic disease. Preoperative colonoscopy was incomplete (only until the splenic angle of the left colon) due to the insufficient mechanical preparation. On laparotomy, a carcinoma of the hepatic angle of the colon, partially stenosing was discovered. An upper pole esogastrectomy with intrathoracic esogastrostomy and a right colectomy with ileotransversostomy were practiced, at the same operative session. Postoperative evolution was poor and the patient died on the ninth day from the surgery during an alcohol withdrawal crisis.

The sentinel lymph node (SLN) significance in colorectal cancer: methods and results. General report.

Colorectal cancer appears to be one of the most important malignancies in the world, with a survival rate depending on the TNM stage. The presence of lymph nodes metastasis indicates the necessity of adjuvant chemotherapy but exact classification of the N stage requires at least 12 lymph nodes to be pathologically examined. The sentinel lymph node (SLN) is considered to be the closest lymph node to the tumor, bearing the highest risk of malignant cells colonization. The main advantage of the sentinel lymph node mapping in colorectal cancer is identification and separate pathological examination of the nodes carrying the highest risk of metastasis. There are still open questions regarding the best method for sentinel lymph node mapping (in vivo or ex vivo), the factors influencing it, which substance is better for identification and which are the best histological methods and markers to be used. Numerous studies have discussed the quality and applicability of the method, but the importance of the SLN in colorectal carcinoma remains an open issue.

c-abl and YWHAZ gene expression in gastric cancer.

This study aims to determine the gene expression for c-abl and YWHAZ in gastric cancer and the differences between the c-abl and YWHAZ gene expression inside the tumor versus healthy tissue (at the resection edges). This prospective study included 34 patients with gastric neoplasia, 21 men and 13 women, aged between 49 and 79 years (65.5 years median). After the surgical procedure, in these cases, we collected two tissue samples: one sample was obtained from inside the tumoral tissue and another sample from the gastric tissue, which was identified as normal apparently, as far as possible from the tumor (resection edge). For determining the c-abl and YWHAZ gene expression, we used the quantitative real-time polymerase chain reaction. Regarding the c-abl gene expression in gastric cancer, c-abl expression was identified as lower inside tumor cells comparing to the normal gastric tissue (resection limit). This difference of gene expression emphasize the role of the c-abl gene in normal tissue growth and the involvement in apoptosis induction when alteration of DNA occurs, as a result to different agents actions as stress, ionizing radiations. The loss of expression or even the down-regulation of the c-abl is a fundamental event that leads to genesis and progression of tumors. No significant differences of the YWHAZ gene expression between the tumoral and normal gastric tissue probes were recorded in our study.

Pyoderma vegetans of the posterior area of the neck: case presentation.

Pyoderma vegetans is a rare disease characterized by the presence of vegetant exudative, pustular and erythematous vesiculobullous plaque usually located in the inguinal area and axillary fold. Etiology of pyoderma vegetans is unknown but it is often associated with bacterial infections in immunocompromised patients. Main histopathological characteristics of pyoderma crops are pseudoepitheliomatous hyperplasia and subepidermal, intraepidermal neutrophilic or eosinophilic microabscesses. It is well known that these lesions are commonly associated with colonic inflammatory disease such as ulcerative colitis and Crohn's disease. Not available standard treatment for pyoderma vegetans, although the use of antibiotic therapy was often used with variable results. Standard first-line therapy is the systemic steroids yet. We perform excision of the lesion of the posterior area of the neck with application of the free split-thickness skin graft after 48 hours postoperatively. In this paper, we present a case of pyoderma vegetans with unusual location without associating colonic lesions and a review of literature related to therapeutic and diagnostic problems of this disease.

Extrarenal retroperitoneal angiomyolipoma with unusual evolution.

The aim of this paper is to present the case of an extrarenal retroperitoneal angiomyolipoma with unusual evolution, due to the herniation through the inguinal canal, determining an extraperitoneal hernia. A ureteral duplicity and associated hydronephrosis contributed to the peculiarity of the case. The case was operated (en block tumor and right kidney removal), the postoperative evolution being favorable at seven years after the surgery.

Collision tumor of recto-sigmoidian junction - case presentation.

Collision tumors of the colon are rare. A 64-year-old man was referred on Emergency County Hospital, Craiova, Romania for the evaluation of intestinal obstruction. Colonoscopy demonstrates the presence of about 9/5 cm sized mass in the rectosigmoid junction. After surgical resection, the rectosigmoid lesion was histopathologically composed of two distinct lesions: mucoid adenocarcinoma in the superficial layer and poorly differentiated neuroendocrin carcinoma in the deeper layer. A rectosigmoid tumor showed two distinct tumors with no admixture or transposition of two neoplastic components. A lymph node metastatic deposit contained both tumors. Immunohistochemical stainings were consistent with mucinous adenocarcinoma and neuroendocrine carcinoma of the two neoplasms. We report this case of colonic collision tumor (mucoid adenocarcinoma and neuroendocrine carcinoma) and review of the literature.

Colorectal cancer - clinical and morphological aspects.

INTRODUCTION: Colorectal cancer (CRC) is one of the most common and most serious malignancies worldwide. Its incidence has increased by more than 200 000 in 2008, both in men and in women. Although CRC is a well-studied malignancy which has a slow progression, known risk factors and pre-neoplastic lesions that can be detected and treated, its incidence is on the rise. In our study, we clinically, histologically and immunohistochemically evaluated a group of 317 patients with colorectal cancer who underwent surgery. PATIENTS AND METHODS: The trial included 317 colorectal cancer patients hospitalized in the second Department of General Surgery within the Emergency County Hospital of Craiova, Romania, between January 2005 and December 2009, aged between 18 and 89 years. After undergoing clinical and laboratory work-up, all patients were submitted to surgery with curative intent. Resection specimens were collected and histological slides were produced from the biological material. Usual histological staining, Hematoxylin-Eosin and trichromic Goldner-Szekely, as well as immunohistochemistry with anti-Ki67, anti-caspase 3, anti-p53 and anti E-cadherin antibodies was also performed. RESULTS: Regarding gender distribution of cases in the study group was a slightly higher incidence in the number of women affected by neoplasia (n=166, 52.35%) than males (n=151, 47.65%). Analysis of incidence per decade of age showed highest figures between 61-70 years, but we also observed comparable values for the decade 51-60 years. Analysis of topography showed higher incidence of cancer of the rectum (119 cases, representing 37.53%) compared to individual segments of the colon. Average size determined for all locations was 5.05 cm, with a median located at 4.82 and a standard deviation of 1.99. Regarding the degree of cell differentiation, out of the total of 245 adenocarcinomas, a number of 87 (35.52%) were well-differentiated adenocarcinomas, 127 (51.83%) were moderately differentiated, and 31 (12.65%) cases were poorly differentiated adenocarcinomas. Index of cell proliferation, Ki67, had a moderate and intense reaction to all the cases studied. Very few tumor cells were immunohistochemically positive for caspase 3, regardless of the degree of tumor differentiation. E-cadherin was intense in well-differentiated adenocarcinomas. In our study, of 42 colon adenocarcinomas, 29 (69%) were highly positive to anti-p53 antibody, the remaining being negative. CONCLUSIONS: Colorectal cancer was diagnosed especially in people over 50 years. Analysis of topography showed higher incidence of cancer of the rectum compared to segments of the colon. More than half were presented in stages III and IV. The histopathological study showed that about 98% of colorectal neoplasms were adenocarcinomas, frequently with moderate differentiation.

Polymer-microporous host interactions probed by photoluminescence spectroscopy.

Zeolites NaY and ZSM-5 were used as hosts for styrene polymerization after ion-exchange with europium ions. The parent and hybrid, polystyrene coated Eu-NaY (Eu-NaY/PS) and Eu-ZSM-5 (Eu-ZSM-5/PS) zeolites were investigated by using thermal analysis, SEM, PXRD, FT-IR, DR-UV/Vis, steady state and time-resolved photoluminescence spectroscopy. FT-IR spectra evidenced for the interaction between the zeolitic hosts and polystyrene while the PXRD spectra supported for the presence of the polymer inside the channels/pores of Eu-NaY/PS and Eu-ZSM-5/PS materials. The optical properties of Eu-NaY/PS and Eu-ZSM-5/PS were significantly changed relative to those of the parent zeolites, giving further evidence for the presence of polymer inside zeolites. An interesting case is presented by NaY zeolite: following styrene polymerization, the polymer interacted selectively with one of the two main species co-existing inside zeolite while for ZSM-5 a similar effect was not observed.

Intestinal pseudo-obstruction--a rare condition with heterogeneous etiology and unpredictable outcome. A case report.

Intestinal pseudo-obstruction (IPO), either acute or chronic, is a condition including features of intestinal ileus in the absence of mechanical obstruction. We present such a rare case of idiopathic IPO in a 53-year old male patient in whom recurrent episodes of pseudo-obstruction were successfully resolved by anticholinesterase agents, motilin agonists or colonic decompression. However, subsequently total colectomy was required. Huge colonic dilatation was identified intraoperatively, while histology evidenced a neuropathic variant of chronic intestinal pseudoobstruction. IPO is a condition in which conservative treatment usually fails. Total colectomy with ileoanal pouch was the solution in our patient.

Intestinal pseudo-obstruction: an uncommon condition with heterogeneous etiology and unpredictable outcome.

Intestinal pseudo-obstruction (IPO) either acute or chronic is a condition including features of intestinal ileus in absence of mechanical obstruction. Our paper presents such a rare case of idiopathic IPO in a 53-year-old male patient with recurrent episodes of pseudo-obstruction, which were successfully resolved by anticholinesterase agents, motilin agonists or colonic decompression. However, the patient finally underwent total colectomy. Huge colonic dilatation was identified intraoperatorily, while histology showed a neuropathic variant of chronic intestinal pseudo-obstruction. Etiologic mechanisms and current therapeutic methods are reviewed in this paper, which concludes that IPO is a condition in which conservative treatment usually fails. Total colectomy with ileoanal pouch may be the only solution in these situations.

Investigation of the hydrophobization efficiency of terbium-exchanged BEA zeolites by means of FT-IR, TGA, physical adsorption, and time-resolved photoluminescence.

Terbium-exchanged BEA zeolites were hydrophobized with phenyl-, vinyl-, and hexadecyltrimethoxysilanes by means of postsynthesis grafting. These materials were investigated using XRD, FT-IR, TGA, physical adsorption, and photoluminescence. Different methods for the analysis of the non-exponential decay of terbium photoluminescence in BEA zeolites were used ranging from discrete exponential to more complex approaches based on maximum entropy and global analysis. Two groups of decay times varying between 480 and 580 micros and 1-1.3 ms were assigned to the lifetimes of terbium exposed to water (unprotected) and protected by the organic groups, respectively. Our results showed that the preservation of terbium PL properties against detrimental effects of moisture adsorption could be ordered in the following sequence: hexadecyl > phenyl approximately vinyl. The photoluminescence results were in good agreement with the FT-IR, TGA, and physical adsorption data.

A particular case of a "captive forceps" in the esophagus.

We present a particular case of a "captive" forceps in the esophagus in an attempt to remove a foreign body in a patient with previous esophageal post-caustic stenosis. The mechanism of incarceration and the surgical therapeutic option consisting of open thoracic surgery are detailed and argumented. Postoperative course was favorable, though the patient developed a small esophageal fistula visible at radiology without any clinical expression. This case emphasizes the difficulties that may occur but in the management of esophageal foreign bodies in patients with esophageal post-caustic stenosis, which may lead finally to open surgery.