3-Aminopyridine Salicylidene: A Sensitive and Selective Chemosensor for the Detection of Cu(II), Al(III), and Fe(III) with Application to Real Samples.

Interest in developing selective and sensitive metal sensors for environmental, biological, and industrial applications is mounting. The goal of this work was to develop a sensitive and selective sensor for certain metal ions in solution. The goal was achieved via (i) preparing the sensor ((E)-2-((pyridine-3-ylimino)methyl)phenol) (3APS) using microwave radiation in a short time and high yield and (ii) performing spectrophotometric titrations for 3APS with several metal ions. 3APS, a Schiff base, was prepared in 5 min and in a high yield (95%) using microwave-assisted synthesis. The compound was characterized by FTIR, XRD, NMR, and elemental analysis. Spectrophotometric titration of 3APS was performed with Al(III), Ba(II), Cd(II), Co(II), Cu(II), Fe(III), Mn(II), Ni(II), and Zn(II). 3APS showed good abilities to detect Al(III) and Fe(III) ions fluorescently and Cu(II) ion colorimetrically. The L/M stoichiometric ratio was 2:1 for Cu(II) and 1:1 for Al(III) and Fe(III). Low detection limits (µg/L) of 324, 20, and 45 were achieved for Cu(II), Al(III), and Fe(III), respectively. The detection of aluminum was also demonstrated in antiperspirant deodorants, test strips, and applications in secret writing. 3APS showed high fluorescent selectivity for Al(III) and Fe(III) and colorimetric selectivity towards Cu(II) with detection limits lower than corresponding safe drinking water guidelines.

Concentrations of essential and toxic elements and health risk assessment in brown rice from Qatari market.

Twenty-two brown rice varieties available in the Qatari market were analyzed for essential and toxic elements by ICP-MS. Found concentrations (µg/kg) were: As: 171 ± 78 (62-343), Cd: 42 ± 60 (4-253), Cr: 515 ± 69 (401-639), Pb: 6 ± 7 ( 1 in million, may possibly be > 1 in 10,000 based on conservatively high brown rice consumption rates of 200 g/d or 400 g/d in Qatar. These elevated risks may be applicable to specific population subgroups with diabetic conditions who consume only brown rice. Non-cancer risks are mainly derived from Mn, V, Se, and Cd with a hazard index > 1 from some brown rice samples.

Diversity of arbuscular mycorrhizal fungi and its chemical drivers across dryland habitats.

Qatar is largely characterized by a hyper-arid climate and low soil fertility which create a stressful soil environment for arbuscular mycorrhizal (AM) fungi. In a study of AM fungal communities and their relationship with soil chemical characteristics, we used a high-throughput sequencing technique to explore AM fungal diversity and community composition in different habitats across Qatar. We identified a total of 79 AM fungal taxa, over 77% of which were species from the Glomeraceae family. The lowest AM fungal diversity was observed in saltmarsh and in one rawdha site, while the highest richness, effective number of species, and diversity were observed in rawdha and sabkha communities. NMDS and multiple regression analyses showed that AM fungi were negatively correlated with soil pH and TC, but positively correlated with K and NO3-. AM fungi also were positively correlated with Cd, with the latter suggesting that very low levels of heavy metals may not always be harmful to AM fungi. These findings provide baseline information on AM fungal assemblages and the chemical drivers of diversity across communities in Qatar. This work partly compensates for the current lack of broad-scale studies in the Arabian Peninsula by providing understanding of overall patterns of AM fungi and their drivers in the region.

Zebrafish larvae as a model to demonstrate secondary iron overload.

OBJECTIVES: Thalassemia is the most common genetically inherited blood disorder arising from a defect in hemoglobin production, resulting in ineffective erythropoiesis and severe hemolytic anemia. While transfusion therapy corrects the anemia, it gives rise to secondary iron overload. Current iron chelation therapy performed using deferoxamine, and the efficiency of this drug was demonstrated here using the zebrafish animal model. METHODS: Zebrafish larvae were exposed for 3 days to iron [100 µmol L-1 ferric ammonium citrate; 3-6 days post fertilization (dpf)]. Then, iron treated larvae were exposed to 100 µmol L-1 deferoxamine for 3 days (6-9 dpf). Total tissue iron concentration in the whole larvae, assessed by three different assays; inductively coupled plasma mass spectrometry, colorimetry (spectrophotometry), and microscopy using iron staining followed by imaging and quantification. RESULTS: The three assays showed that iron treatment alone resulted in a significant increase in total iron. Deferoxamine treatment of the iron-loaded zebrafish larvae showed a significant decrease in total iron concentration. CONCLUSION: This study presented a clear evidence of the effectiveness of zebrafish larvae to use as a tool to study iron overload and open the door for studying the efficiency of potential new iron chelating compounds other than commercially available ones.

Aerobic sludge granulation at high temperatures for domestic wastewater treatment.

With inoculum sludge from a conventional activated sludge wastewater treatment plant, three sequencing batch reactors (SBRs) fed with synthetic wastewater were operated at different high temperatures (30, 40 and 50±1°C) to study the formation of aerobic granular sludge (AGS) for simultaneous organics and nutrients removal with a complete cycle time of 3h. The AGS were successfully cultivated with influent loading rate of 1.6CODg(Ld)(-1). The COD/N ratio of the influent wastewater was 8. The results revealed that granules developed at 50°C have the highest average diameter, (3.36mm) with 98.17%, 94.45% and 72.46% removal efficiency observed in the system for COD, ammonia and phosphate, respectively. This study also demonstrated the capabilities of AGS formation at high temperatures which is suitable to be applied for hot climate conditions.

Dental clinics: a point pollution source, not only of mercury but also of other amalgam constituents.

Current literature suggests that amalgam waste from dental clinics is a point-source of mercury pollution in the environment. However, apart from mercury, other amalgam constituents (e.g. Ag, Sn, Cu, and Zn) in dental clinics' wastewater have not been reported in the literature before. The objective of this study was to evaluate the concentrations of mercury and other metals in the wastewater of some dental clinics and the influent of a wastewater treatment plant in Al-Madinah Al-Munawarah (KSA). Samples were collected over a 2-month period from three dental clinics and analyzed for metals using ICP-MS. The mean concentrations of Hg, Ag, Sn, Cu, and Zn in the samples were 5.3±11.1, 0.49±0.96, 3.0±10.7, 10.0±14.5, and 76.7±106 mg L(-1), respectively. Additionally, high concentrations of other metals such as Mg (14.4±15.2 mg L(-1)), Mn (3.0±4.6 mg L(-1)), Fe (3.0±4.5 mg L(-1)), Sr (1.6±2.4 mg L(-1)), and Ba (6.9±10.3 mg L(-1)) were also found. These values are much higher than the local permissible limits. Most of the metals of interest were also detected in the influent of the wastewater treatment plant. This renders dental clinics wastewater a hazardous waste which should be properly treated before it is discharged into the environment.

A randomised intervention trial to assess two arsenic mitigation options in Bangladesh.

Arsenic groundwater contamination in Bangladesh warrants immediate remediation. This randomised controlled intervention trial was conducted to determine the effectiveness of two possible interventions: dug wells and three-pitcher filters. A total of 640 individuals participated with 218 randomised to the dug well group, 216 to the three-pitcher group and 206 to a control group. Data were collected at baseline and at 1, 6 and 12 months after the intervention. Self reported compliance with dug wells remained below 20% during the entire 12 months of the study. The compliance with the three-pitcher filters decreased after 6 months and became similar to the compliance of the dug well group after 12 months. A substantial decrease in urinary arsenic metabolites occurred only among those who were compliant with dug wells and three-pitcher filter systems after 1 month of intervention as opposed to control participants. However, a persistent reduction in urinary arsenic concentrations was observed only among the dug well users after 12 months of intervention. Our results show that a functional dug well could be offered as a long-term alternative to tube wells, but use of this option is likely to be low, unless appropriate behavioural change measures are taken. Our study also demonstrates that arsenic removal technologies such as three-pitcher filters are an effective option as a short-term measure. The three-pitcher filters that are not adequately maintained are not an effective option for a year. These arsenic removal technologies may be even harmful in the long term if the resultant water quality is not properly monitored.

Imidacloprid residues in fruits, vegetables and water samples from Palestine.

The aim of this work was to report on imidacloprid [IUPAC name 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] residues in some vegetables, fruits, and water samples collected from the West Bank, Palestine, in 1998 and 1999. Imidacloprid and its derivatives in the study samples were extracted by methanol/water and oxidized into 6-chloronicotinic acid and subsequently derivatized into 6-chloronicotinic acid trimethylsilyl ester before being determined by GC/MS. Imidacloprid residues were detected in more than half of the analyzed samples. The highest and lowest imidacloprid concentrations were found in eggplant (0.46 mg/kg) and green beans (0.08 mg/kg), respectively. An increase of 11-120% in imidacloprid concentration in the 1999 samples was observed when compared with those of 1998. This may suggest imidacloprid accumulation in the soil and/or increased use by local farmers. The imidacloprid residue concentrations in several crops were found to exceed the CODEX maximum residue limit.

Accumulation and toxicity of monophenyl arsenicals in rat endothelial cells.

Clark 1 (diphenylarsine chloride) and Clark 2 (diphenylarsine cyanide) were used as chemical weapon agents (CWA), and the soil contamination by these CWA and their degraded products, diphenyl and phenyl arsenicals, has been one of the most serious environmental issues. In a series of comparisons in toxicity between trivalent and pentavalent arsenicals we investigated differences in the accumulation and toxicity of phenylarsine oxide (PAO3+) and phenylarsonic acid (PAA5+) in rat heart microvascular endothelial cells. Both the cellular association and toxicity of PAO3+ were much higher than those of PAA5+, and LC50 values of PAO3+ and PAA5+ were calculated to be 0.295 microM and 1.93 mM, respectively. Buthionine sulfoximine, a glutathione depleter, enhanced the cytotoxicity of both PAO3+ and PAA5+. N-Acetyl-L-cysteine (NAC) reduced the cytotoxicity and induction of heme oxygenase-1 (HO-1) mRNA in PAO3+-exposed cells, while NAC affected neither the cytotoxicity nor the HO-1 mRNA level in PAA5+-exposed cells. The effect of NAC may be due to a strong affinity of PAO3+ to thiol groups because both NAC and GSH inhibited the cellular accumulation of PAO3+, but PAA3+ increased tyrosine phosphorylation levels of cellular proteins. These results indicate that the inhibition of protein phosphatases as well as the high affinity to cellular components may confer PAO3+ the high toxicity.

The accumulation and toxicity of methylated arsenicals in endothelial cells: important roles of thiol compounds.

Excess intake of arsenic is known to cause vascular diseases as well as skin lesions and cancer in humans. Recent reports suggest that trivalent methylated arsenicals, which are intermediate metabolites in the methylation process of inorganic arsenic, are responsible for the toxicity and carcinogenicity of environmental arsenic. We investigated acute toxicity and accumulation of monomethylarsonic acid (MMA(V)), dimethylarsinic acid (DMA(V)), trimethylarsine oxide (TMAO), and monomethylarsonous acid diglutathione (MMA(III) (GS)(2)) in rat heart microvessel endothelial (RHMVE) cells. MMA(V) (LC(50) = 36.6 mM) and DMA(V) (LC(50) = 2.54 mM) were less toxic than inorganic arsenicals (cf. LC(50) values for inorganic arsenite (iAs(III)), and inorganic arsenate (iAs(V)) was reported to be 36 and 220 microM, respectively, in RHMVE cells. TMAO was essentially not toxic. However, MMA(III) (GS)(2) was highly toxic (LC(50) = 4.1 microM). The order of cellular arsenic accumulation of those four organic arsenic compounds was MMA(III) (GS)(2) >> MMA(V) > DMA(V) > TMAO. MMA(III) (GS)(2) was efficiently taken up by the cells and cellular arsenic content increased with the concentration of MMA(III) (GS)(2) in culture medium. N-acetyl-l-cysteine (NAC) reduced cellular arsenic content in DMA(V)-exposed cells and also decreased the cytotoxicity of DMA(V), whereas it changed neither cellular arsenic content nor the viability in MMA(V)-exposed cells. mRNA levels of heme oxygenase-1 (HO-1) were decreased by NAC in DMA(V)-exposed, but MMA(V)-exposed cells. Buthionine sulfoximine (BSO), a cellular glutathione (GSH) depleting agent, enhanced the cytotoxicity of MMA(V). However, BSO reduced, rather than enhanced, the cytotoxicity of DMA(V). These results suggest that intracellular GSH modulated the toxic effects of arsenic in opposite ways for MMA(V) and DMA(V). Even though intracellular GSH decreased the cytotoxicity of MMA(V), extracellularly added GSH enhanced the cytotoxicity of MMA(V). The use of high-performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometric analyses suggested that a small amount of MMA(V) was converted to MMA(III) (GS)(2) in the presence of GSH. These results suggest that MMA(III) (GS)(2) is highly toxic compared to other arsenic compounds because of faster accumulation of this species by cells, in addition to having the toxic nature of methylated trivalent organic arsenics.

Subchronic exposure to arsenic through drinking water alters expression of cancer-related genes in rat liver.

Although arsenic exposure causes liver disease and/or hepatoma, little is known about molecular mechanisms of arsenic-induced liver toxicity or carcinogenesis. We investigated the effects of arsenic on expression of cancer-related genes in a rat liver following subchronic exposure to sodium arsenate (1, 10, 100 ppm in drinking water), by using real-time quantitative RT-PCR and immunohistochemical analyses. Arsenic accumulated in the rat liver dose-dependently and caused hepatic histopathological changes, such as disruption of hepatic cords, sinusoidal dilation, and fatty infiltration. A 1-month exposure to arsenic significantly increased hepatic mRNA levels of cyclin D1 (10 ppm), ILK (1 ppm), and p27(Kip1) (10 ppm), whereas it reduced mRNA levels of PTEN (1 ppm) and beta-catenin (100 ppm). In contrast, a 4-month arsenic exposure showed increased mRNA expression of cyclin D1 (100 ppm), ILK (1 ppm), and p27(Kip1) (1 and 10 ppm), and decreased expression of both PTEN and beta-catenin at all 3 doses. An immunohistochemical study revealed that each protein expression accords closely with each gene expression of mRNA level. In conclusion, subchronic exposure to inorganic arsenate caused pathological changes and altered expression of cyclin D1, p27(Kip1), ILK, PTEN, and beta-catenin in the liver. This implies that arsenic liver toxicity involves disturbances of some cancer-related molecules.

A global health problem caused by arsenic from natural sources.

Arsenic is a carcinogen to both humans and animals. Arsenicals have been associated with cancers of the skin, lung, and bladder. Clinical manifestations of chronic arsenic poisoning include non-cancer end point of hyper- and hypo-pigmentation, keratosis, hypertension, cardiovascular diseases and diabetes. Epidemiological evidence indicates that arsenic concentration exceeding 50 microg l(-1) in the drinking water is not public health protective. The current WHO recommended guideline value for arsenic in drinking water is 10 microg l(-1), whereas many developing countries are still having a value of 50 microg l(-1). It has been estimated that tens of millions of people are at risk exposing to excessive levels of arsenic from both contaminated water and arsenic-bearing coal from natural sources. The global health implication and possible intervention strategies were also discussed in this review article.

Difference in uptake and toxicity of trivalent and pentavalent inorganic arsenic in rat heart microvessel endothelial cells.

Intake of inorganic arsenic is known to cause vascular diseases as well as skin lesions and cancer in humans. We investigated the differences in cytotoxicity, uptake rate of arsenic, and gene expression of antioxidative enzymes between arsenite (As(3+))- and arsenate (As(5+))-exposed rat heart microvessel endothelial cells. As(3+) was more cytotoxic than As(5+), and LC(50) values were calculated to be 36 and 220 micro M, respectively. As(3+) (1-25 micro M) increased mRNA levels of antioxidant enzymes such as heme oxygenase-1 (HO-1), thioredoxin peroxidase 2, NADPH dehydrogenase, and glutathione S-transferase P subunit. HO-1 mRNA levels showed the most remarkable increase in response to As(3+). cDNA microarray analysis indicated that there was no prominent difference in arsenic-induced transcriptional changes between As(3+)- and As(5+)-exposed cells, when the cells were exposed to one-fourth the LC(50) concentration of arsenic (9 and 55 micro M for As(3+) and As(5+), respectively). N-acetyl- l-cysteine (NAC) reduced both the cytotoxicity of inorganic arsenic and the HO-1 mRNA level, and buthionine sulfoximine enhanced cytotoxicity of inorganic arsenic. As(3+) was taken up by the endothelial cells 6-7 times faster than As(5+), and the presence of NAC in the culture medium did not change the uptake rate of As(3+). These results suggest that the effects of NAC on arsenic-induced cytotoxicity and oxidative stress were due to the antioxidative role of non-protein thiols and not to chelation of arsenic in the culture medium. The difference in cellular uptake of arsenic between As(3+) and As(5+) appeared not to be due to the ionic charge on arsenic (at physiological pH, trivalent arsenic is neutral whereas pentavalent arsenic is negatively charged). These results suggest that the higher toxicity of As(3+) compared with that of As(5+) is probably due to the faster uptake of As(3+) by endothelial cells, and inorganic arsenic exerts its toxicity at least in part via intracellular oxidative stress.

Arsenic speciation in the urine and hair of individuals exposed to airborne arsenic through coal-burning in Guizhou, PR China.

The extent of exposure of residents of Changqing (Guizhou, PR China) to arsenic through coal-burning was investigated. Despite the low coal-arsenic content (56.3+/-42.5 mg As kg(-1)) when compared with coals collected at different location and times from the same province, more than 30% of the study subjects have shown symptoms of arsenicosis. Coal, urine, hair, and water samples were collected in mid-September 2001 and analysed for arsenic. The average urinary and hair-arsenic concentrations in the exposed subjects were 71.4+/-37.1 microg As g(-1) creatinine (control 41.6+/-12.1) and 7.99+/-8.16 mg kg(-1), respectively. A positive correlation between the hair and urinary-arsenic concentration (R(2)=0.601) was found. There was no significant difference between females and males for both urinary and hair-arsenic concentrations. Females were found to have a higher dimethylarsinic acid but lower percentages of inorganic arsenic and monomethylarsonic acid in their urine than males.