Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in sewage gas by using cryotrapping gas chromatography inductively coupled plasma mass spectrometry

Evidence for the occurrence of Ni(CO)4 in addition to Mo(CO)6 and W(CO)6 in fermentation gases from a municipal sewage treatment plant is presented for the first time. The gases were sampled at the top of the sewage sludge digester using Tedlar bags, and were analysed using cryotrapping followed by gas chromatography coupled with inductively coupled mass spectrometry (GC-ICP-MS). The use of an ICP-MS as an element-specific detector gives sufficiently low detection limits for metals and was coupled to a packed column gas chromatograph. This method provides information about the speciation of volatile transition metals in contrast to previously used methods for the determination of Ni(CO)4 in gas samples. The element-specific detection of three different isotopes (m/z 58, 60, 62) and the correspondence of the samples' retention times with those of the standard provided convincing evidence that Ni(CO)4 is present in the fermentation gas. The concentrations found were in the sub-ppb level, which is at least one order of magnitude lower than the threshold level of 1 ppb (v/v). In addition, Mo(CO)6 and W(CO)6 were also measured in the sub-ppb range in contrast to the absence of Fe(CO)5. The stabilities of Ni(CO)4, Fe(CO)5, and Mo(CO)6 were tested in a carbon monoxide atmosphere. In the presence of distilled water, the following order of stability was found after 11 weeks: Fe(CO)5 < Ni(CO)4 < Mo(CO)6. In the presence of an aqueous solution containing nickel, molybdenum, tungsten and iron, however, only Fe(CO)5 was significantly decomposed (< 0.3% recovery); Ni(CO)4 and Mo(CO)6 were stable after 11 weeks. No W(CO)6 was formed. The low stability of Fe(CO)5 in the presence of water could be the reason why no volatile iron compound was found in sewage gas. This study showed that GC-ICP-MS can be employed to identify species-specific traces of metal carbonyls in process gases such as sewage gas.     

Spatial distribution of trace metals (Cd, Pb, Hg, Cu, Zn, Fe and Mn) and oligo-elements (Mg, Ca, Na and K) in surface sediments of the Gulf of Tunis (Northern Tunisia)

The purpose of this paper is to evaluate the levels and spatial distribution of trace metals (Cd, Pb, Cu, Hg, Zn, Fe, and Mn), oligo-elements (Mg, Ca, Na and K), total organic carbon (TOC), and total nitrogen (TN) in the fine fraction of surface sediments collected from 38 stations in Gulf of Tunis (Mediterranean Sea, Northern Tunisia) between 2004 and 2005. The results showed that metals, oligo-elements, TOC, and TN concentrations in the sediments of the Gulf of Tunis are generally low compared to those found in other similar coastal marine areas. The spatial distribution of metals showed areas of major accumulation of Pb, Cd, Cu, Fe, and Zn in the central area of the Gulf and near the Mejerda River. The marine currents are influencing factors on metal accumulation in sediments. The principal component analysis applied to our elemental analytical results showed that there is a positive correlation between Fe, Zn, Cu, and Pb. These metals have a stronger affinity with site connection in the sediments than Ca and Mn.     

Biomonitoring of heavy metals (Cd,Hg, and Pb) and metalloid (As) with the Portuguese common buzzard (Buteo buteo)

The accumulation of heavy metals in the environment may have a wide range of health effects on animals and humans. Thus, in this study, the concentrations of arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg) in the blood and tissues (liver and kidney) of Portuguese common buzzards (Buteo buteo) were determined by inductively coupled plasma-mass spectrometer (ICP-MS) in order to monitor environmental pollution to these elements. In general, Hg and As were the elements which appeared in the highest and lowest concentrations, respectively. A highest percentage of non-detected concentration was found for blood Cd (94.6 %) but, in turn, it was the only metal that was detected in all kidney samples. The kidney was the analyzed sample which showed the highest concentrations of each element evaluated. Statistically, significant differences among blood, liver, and kidney samples were observed for As and Cd (P?相似文献   

Seasonal and Interannual Variations in the Frequency and Severity of Deformities in Larvae of Chironomus riparius (Meigen, 1804) and Prodiamesa olivacea (Meigen, 1818) (Diptera, Chironomidae) collected in a polluted site

Larvae of Chironomus riparius and Prodiamesa olivacea were sampled at intervals overthe period November 1993 and October 1995 from theriver Sar in Galicia (N.W. Spain), with the aim ofinvestigating possible temporal variations in thefrequency of deformed individuals and in `Toxic Score'values (Lenat, 1993), a score for severity of theabnormalities calculated for each species. The resultsobtained indicate that, in both species, deformitiesare more frequent during the colder period of theyear. Similarly, Toxic Score values are higher duringthis period. These finding suggest that studies usingchironomid larvae as indicators of contaminationsshould involve sampling over an extended period, tominimize the influence of temporal variation.     

Chemical speciation and partitioning of trace metals (Cd, Co, Cu, Ni, Pb) in the lower Athabasca river and its tributaries (Alberta, Canada)

Concentrations of Cd, Co, Cu, Ni and Pb were measured in particulate and dissolved phases at 11 sites located upstream and near Athabasca oil sands development. The in situ discrimination between non-labile and labile dissolved metals was done using diffusive gradients in thin-films (DGT) devices. The DGT-labile fraction of Co and Ni was 30% lower near development sites whereas Cu, Cd and Pb showed minor changes spatially. It was found that an 8-fold increase in dissolved organic matter (DOM) near development induced a rapid decrease in DGT-labile metals. Dissolved metal concentrations were used along with DOM, major ions, nutrients, pH and conductivity to calculate the distribution of dissolved metal species using the speciation model WHAM. Labile-DGT metal concentrations agreed well with WHAM-predicted concentrations. It was also found that a significant amount of metals were associated with the non-DGT labile fraction (i.e. colloidal DOM) and colloid abundance was more important than suspended particulate matter abundance in influencing metal mobility near Athabasca oil soils development. Since changes in colloidal DOM levels are likely to be the result of surface mining activities, this confirms the serious effects of oil sands activities on metal biogeochemical cycles in the lower Athabasca River.     

Toxic metal (Pb, Cd, As and Hg) and organochlorine residue levels in hake (Merluccius merluccius) from the Marmara Sea, Turkey

Toxic metals (Pb, Cd, As and Hg) and organochlorine residue levels were measured in hake (Merluccius merluccius) from the Marmara Sea. Biota samples were collected by a trawling cruise of the R/V ARAR in August and December 2009. The concentrations of toxic metals varied between Pb, 3.23-14.4; Cd, <0.01-2.14; Hg, 0.01-0.18 and As, 0.01-0.21 [Formula: see text]g g(-1) dry wt. Pb levels in the Marmara Sea were found to be higher than the critical limits set by the both Turkish Ministry of Environment for Aquatic Products (1 μg g(-1) wet wt.) and European countries (2.0 μg g(-1), UNEP 1985). In contrast, As and Hg levels were found to be lower than the critical limits for two periods. Cd contents of fish from the Marmara Sea were also comparable to or slightly lower than contents of fish from the Southern Black Sea Shelf. The results of organochlorine residues ranged between total HCH, <0.05 and 99 ng g(-1); endrin, <0.001 and 381 ng g(-1); alpha-endosulphan, <0.05 and 90 ng g(-1); beta-endosulphan, <0.05 and 15.3 ng g(-1); o,p DDE, 3.5 and 52.4 ng g(-1); p,p DDE, 7.4 and 139 ng g(-1); o,p DDD, 1.5 and 90.2 ng g(-1) and p,p DDD, 2.7 and 86 ng g(-1) wet weight. The rivers for the distribution of organochlorine levels in the Marmara Sea ordered from highest to lowest as Dil R. > Susurluk R. > Biga R. > G?nen R. The high levels of o,p and p,p DDE, and o,p and p,p DDD compounds, which are metabolites of DDT, indicate its illegal use. Toxic metal and organochlorine residue levels of fish are significantly higher than levels from the Mediterranean Sea.     

Heavy metals in water and in tissues of himri (Carasobarbus luteus) from Orontes (Asi) River, Turkey

Concentrations of heavy metals (Ag, Cd, Cr, Cu, Fe, Ni, Pb ve Zn) were measured in running water and in tissues (muscle, liver, gill, skin and gonads) of one commercially valuable fish species (Carasobarbus luteus) from the Orontes (Asi) River (Güzelburç region) in Hatay (Southeastern Turkey). Results for levels in water compared with national and international water quality guidelines were found at the highest concentrations in international criteria’s WHO, EC and EPA, but Cd, Cu, Ni and Pb were found to exceed permissible level of drinking water in national criteria TSE-266 whereas Fe, Zn and Cr concentrations were within the permissible levels for drinking. The present study showed a significant seasonal variation (p?p?>?0.05), which showed seasonal variation of only Zn (p?C. luteus were below the permissible limit for human consumption, level of Cu being very close to the permissible limit. Consequently, continuous monitoring of heavy metal concentration in edible freshwater fish will be needed in Orontes River.     

Monitoring toxic cyanobacteria and cyanotoxins (microcystins and cylindrospermopsins) in four recreational reservoirs (Khon Kaen, Thailand)

The toxic cyanobacterial communities of four recreational reservoirs (Bueng Kaen Nakhon, Bueng Thung Sang, Bueng Nong Khot, and Bueng See Than) in Amphur Muang, Khon Kaen Province, Thailand, were investigated. Water samples were collected via monthly sampling from June to October 2011 for the study on the diversity and density of toxic cyanobacteria and toxin quantification. The main toxic cyanobacteria present in these reservoirs were Aphanocapsa sp., Cylindrospermopsis sp., Leptolyngbya sp., Limnothrix sp., Microcystis sp., Oscillatoria sp., Planktolyngbya sp., Planktotrix sp., and Pseudanabaena sp. The dominant bloom-forming genera in the water samples from Bueng Nong Khot and Bueng See Than were Microcystis sp. and Cylindrospermopsis sp., respectively. Enzyme-linked immunosorbent assays specific for cyanotoxins were performed to detect and quantify microcystins and cylindrospermopsins, with the highest average microcystins content (0.913 μgL^?1) being found in the sample collected from Bueng Nong Khot and the highest average cylindrospermopsins content (0.463 μgL^?1) being found in the sample collected from Bueng See Than. The application of 16S rRNA analyses to cyanobacterial isolates BKN2, BNK1, BNK2, and BST1 indicated that these isolates are most closely related to Limnothrix planctonica (JQ004026) (98 % similarity), Leptolyngbya sp. (FM177494) (99 % similarity), Microcystis aeruginosa (DQ887510) (99 % similarity), and Limnothrix redekei (FM177493) (99 % similarity), respectively.     

Spectrophotometric determination of platinum(IV) in alloys, complexes, environmental, and pharmaceutical samples using 4-[N,N-(diethyl)amino] benzaldehyde thiosemicarbazone

4-[N,N-(Diethyl)amino] benzaldehyde thiosemicarbazone (DEABT) is proposed as an analytical reagent for the spectrophotometric determination of platinum(IV). The DEABT forms 1:2 yellow complex with Pt(IV), which is sparingly soluble in water and completely soluble in water–ethanol–DMF medium. The Pt(IV)–DEABT complex shows maximum absorbance at 405 nm. Beer’s law is valid up to 7.80 μg cm^???3, and optimum concentration range for the determination of platinum(IV) is 0.48–7.02 μg cm^???3. The molar absorptivity and Sandell’s sensitivity of the method are found to be 1.755 × 10⁴ dm³ mol^???1 cm^???1 and 0.0012 μg cm^???2, respectively. The relative error and coefficient of variation (n?=?6) for the method does not exceed ±0.43% and 0.35%, respectively. Since the method tolerates a number of metal ions commonly associated with platinum, it can be employed for the determination of platinum in environmental samples, pharmaceutical samples, alloys, catalysts, and complexes. The method is rapid as the Pt(IV)–DEABT complex is soluble in water–ethanol–DMF medium and not requiring any time consuming extraction method for the complex.     

Mercury Contamination of the EEL (Anguilla Anguilla) and Roach (Rutilus Rutilus) in East Anglia, UK

The muscle tissue total mercury (THg) and organomercury (OrHg) concentrations of eel (Anguilla anguilla) and roach (Rutilus rutilis) from the Hg-contaminated River Yare and the uncontaminated Ormesby Broad were compared to their respective bed sediment THg and OrHg concentrations in order to determine if fish in the River Yare had begun to approach 'background' levels. While eel from the Yare had higher flesh concentrations (260 g kg-1) than those from Ormesby Broad (102 g kg- 1), roach were found to have similar concentrations regardless of location (55 and 54 g kg-1 for Yare and Ormesby respectively). However, roach in the Yare had significantly higher body burdens of Hg and organomercury, which when analysed over time (1985–95) showed a decreasing trend approaching the levels observed in fish from Ormesby Broad, suggesting that roach are an overall better biomonitor of contamination then eel. This said, the elevated levels of Hg found in fish from Ormesby Broad indicate the existence of a diffuse source such as atmospheric deposition to the surface waters of East Anglia.     

我国4个大城市空气PM_(2.5)、PM_(10)污染及其化学组成

报告了 1 995～ 1 996年在中国的广州、武汉、兰州、重庆 4大城市 8个采样点 PM2 .5 、PM2 .5～ 1 0 和 PM1 0 的监测结果。结果表明 ,1 995年 PM2 .5 年均值浓度为 57～ 1 60 μg/m3,比美国 1 997年颁布的标准值 (1 5μg/m3)高 2 .8～ 9.7倍。PM1 0 年日均值为 95～ 2 73μg/m3。除武汉市 1个对照点外 ,其余 7个监测点的 PM1 0 均超过我国空气质量二极标准 (1 0 0μg/m3)2 8%～ 1 73 % ,比美国标准 (50μg/m3)超过更多 ,说明污染是相当严重的。用 XRF分析了 PM2 .5 、PM2 .5～ 1 0 中 4 2种化学元素 ,结果表明 ,燃煤、燃油和其它工业污染的元素 As、Pb、Se、Zn、Cu、Cl、Br、S在这些颗粒物中有明显富集 ,特别是在PM2 .5 中的富集倍数达数十倍至数万倍 ,对人体健康有很大危害     

Metals in marine environment (mollusc Patella sp., fish Labrus bergylta, crustacean Cancer pagurus, beach sand) in a nuclear area, the North Cotentin (France)

The results of a 1-year long survey of trace metals concentrations (Al, Cd, Cr, Co, Cu, Fe, Mn, Hg, Ni, Pb, Zn) measured in beach sand, limpets and, occasionally, in fish and shellfish from the North Cotentin area (France), where nuclear industries are implanted, are presented. The objective of these study was to provide useful data for the validation of models predicting the impact of these industries on the marine environment. Even if differences were noted between sites for various metals, the levels are consistent with existing data published for similar site and do not appear to give evidence of contamination by industrial sites.     

Concentrations, sources, and exposure profiles of polycyclic aromatic hydrocarbons (PAHs) in particulate matter (PM10) in the north central part of India

Airborne particulates (PM₁₀) from four different areas within Agra city (a semi-arid region) were collected using respirable dust samplers during the winter season (Nov. 2005–Feb 2006) and were then extracted with methylene chloride using an automated Soxhlet Extraction System (Soxtherm^®). The extracts were analyzed for 17 target polycyclic aromatic hydrocarbons (PAHs) and the heterocycle carbazole. The average concentration of total PAH (TPAH) ranged from 8.04 to 97.93 ng m^???3. The industrial site had the highest TPAH concentration followed by the residential, roadside, and agricultural sites. Indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, and benzo(b)fluoranthene were the predominant compounds found in the samples collected from all of the sites. The average B(a)P-equivalent exposure, calculated by using toxic equivalent factors derived from literature and the USEPA, was approximately 7.6 ng m^???3. Source identification using factor analysis identified prominent three, four, four, and four probable factors at industrial, residential, roadside, and agricultural sites, respectively.     

Mass occurrence of the ctenophore Bolinopsis vitrea (L. Agassiz, 1860) in the nearshore southern Adriatic Sea (Kotor Bay, Montenegro)

The ctenophore Bolinopsis vitrea has been rarely observed in the Mediterranean Sea. A bloom of B. vitrea is here reported for the first time in the southern Adriatic Sea in the spring and summer of 2009, together with its effect on the plankton of Kotor Bay. Ctenophores were found below 5 m depth only. Results of the investigation indicate that mass occurrence of B. vitrea could have a great impact on the Kotor Bay ecosystem. Their predation on copepods would reduce grazing pressure on phytoplankton, favouring an uncommon bloom of the latter. It is evident that B. vitrea are capable of altering rapidly the composition and biomass of coastal plankton communities when present in large masses. This first evidence of such events for this species may indicate changes in the functioning of marine ecosystems of the southern Adriatic.     

Polycyclic aromatic hydrocarbons in clams Ruditapes decussatus (Linnaeus, 1758)

The concentration of sixteen individual polycyclic aromatic hydrocarbons (PAHs) was measured in the clam Ruditapes decussatus whole soft tissues from several places of the Ria Formosa lagoon (Portugal). Total PAH (tPAH) concentrations were higher in the summer (August) and winter (January) than in the other months and the distribution pattern of the individual PAHs was generally dominated by the 4 aromatic ring PAHs, followed by the 2 + 3 aromatic rings PAHs. Benzo[a]anthracene and acenaphthene were the most representative PAHs of the two fractions. Principal components analysis (PCA) revealed that, in the Ria Formosa, seasonal variations are more important than spatial variations, due to changes in PAH source. These sources ranged from petrogenic to pyrolytic or a mixture of both. The origin of clam PAHs was also assessed by partial least squares (PLS) analysis using nineteen different PAH signatures, taken from the literature. It was possible to identify boat traffic, especially in the summer, as one of the most relevant PAH sources to the Ria Formosa. The influence of boat traffic was revealed by several signatures including diesel soot, oil and weathered oil and a mixture of different individual PAHs usually found in harbour sediments. Other relevant sources included combustion of organic matter such as forest fires and diverse domestic activities, occurring mainly in the summer. Most of the clams were considered safe for human consumption, except for some point samples, which presented unusually high PAH concentrations, suggesting the need for a regular survey of PAHs in clam tissues.     

Effects of Cadmium (CdCl2) on development and hatching of eggs in European squid (Loligo vulgaris Lamarck, 1798) (Cephalopoda: Loliginidae)

This is the first study related to the effects of cadmium (Cd) on the development and hatching of eggs of Loligo vulgaris. The eggs were exposed to concentrations varying from 10 to 100,000 μg Cd/l for up to 1 month. During the study period natural sea water salinity (37 PSU), ambient temperature (ranging 16.5–21.5°C) and light conditions of 12-h light: 12-h dark for 744-h were used prior to the hatching. For 96-h, mortality rate of 100% of the eggs was found at cadmium concentration of 100,000 μg Cd/l, and the same mortality rate of the eggs were found at 1,000 and 10,000 μg Cd/l for 744-h and 696-h, respectively. Hatching took place between hours 456 and 576 in the control group and between hours 480 and 576 in 10 and 100 μg Cd/l groups. Total hatching rates were calculated to be 98.2 ± 1.6% for control group, 99.4 ± 0.6% for 10 μg Cd/l group and 98.6 ± 1.2% for 100 μg Cd/l group. Hatching successes were estimated as 69.5 ± 13.8% for control group, 84.5 ± 8.2% for 10 μg Cd/l group and 76.9 ± 5.9% for 100 μg Cd/l group. In the 100,000 μg Cd/l treatment, the egg degeneration began from animal pole of the eggs in 16 h, and 50% and 100% of them died in the initial stage at 72-h and 96-h, respectively. In the 10,000 μg Cd/l group, the eggs which reached at stage 19 (IX) were deformed and 50% and 100% of them died at 312-h and 696-h, respectively. In 1,000 μg Cd/l group, however, the eggs developed abnormally from stage 21 (X–XI) and reached at stage 29 (XIX), and 50% and 100% of them died in 624-h and in 744-h, respectively. There were significant differences in survival rates of the eggs among the concentrations (p < 0.05). The current study demonstrated that Cd adversely affects the development, survival and hatching of L. vulgaris eggs; however, no mortality was observed in 10 μg Cd/l and 100 μg Cd/l groups.     

Carbon, nitrogen, and phosphorus budget in scampi (Macrobrachium rosenbergii) culture ponds

Experiments were conducted for the study of nutrient budget in ten farmer's ponds (0.2–0.5 ha) in Orissa, India with a mean water depth of 1.0–1.2 m. Scampi (Macrobrachium rosenbergii) were stocked in these ponds at stocking density of 3.75–5.0/m². The average initial body weight of scampi was 0.02 mg. The culture period was for 4 months. Feed was the main input. Total feed applied to these ponds ranged from 945 to 2261 kg pond/cycle (crop). The feed conversion ratio varied 1.65 to 1.78. In addition to feed, rice straw, urea, and single super phosphate were applied to these ponds in small amounts for plankton production. At harvest time, the average weight of scampi varied from 60–90 g. The budget showed that feed was the major input of nitrogen (N), phosphorus (P), and carbon in these ponds. The inorganic fertilizer (urea and single super phosphate), organic fertilizer (rice straw and yeast extract), and inlet water, either from the initial fills or from rainwater, were the source of all other N, P, and organic carbon (OC) to these ponds. Total N applied to these ponds through all these inputs ranged from 44.45 to 103.98 kg N per crop, 12.23 to 28.79 kg P per crop, and from 381.54 to 905.22 kg OC per crop, respectively. Among all the inputs, feed alone accounted for 95.34 % N, 97.98 % P, and 94.27 % OC, respectively. Recovery of 16.34 to 38.66 kg N (average 29.27 kg), 1.28 to 3.02 kg P (average 2.29 kg), and 63.21 to 149.51 kg OC (average 113.20 kg), respectively, by the scampi harvest were observed in these ponds. Thus, harvest of scampi accounted for recovery of 35.18 to 39.01 (average 36.85 %) of added N, 10.09 to 10.97 (average 10.44 %) of added P, and 7.57 to 17.12 (average 16.34 %) of added OC, respectively.     

Heavy metals in Patella caerulea (Mollusca, Gastropoda) in polluted and non-polluted areas from the Iskenderun Gulf (Mediterranean Turkey)

The concentrations of Cd, Cu, Zn, Fe, Pb, Ni, and Co were measured in gastropod mollusks Patella caerulea in the Mediterranean area. The organisms were collected at two coastal sites in Iskenderun Gulf during winter, spring, summer, and autumn 2008. Samples of the digestive gland, gill, and muscle were analyzed for heavy metals. The aim of study is to determine heavy metal levels in tissues of P. caerulea in different locations. Tissues of P. caerulea from the polluted site showed metal concentrations appreciably higher than unpolluted organisms. The highest metal levels were registered in the digestive gland of P. caerulea. Generally, digestive gland and gills showed higher metal concentrations than muscle. The average concentrations of heavy metals analyzed exhibited the following decreasing order: Fe > Zn > Cu > Ni > Cd > Pb > Co for both stations 1 and 2. Seasonal changes in metal concentrations were observed in the tissues of P. caerulea from a polluted and an unpolluted population.     

Concentration of four heavy metals (cadmium, lead, mercury, and arsenic) in organs of two cyprinid fish (Cyprinus carpio and Capoeta sp.) from the Kor River (Iran)

Concentration of heavy metals in aquatic animals mainly occurs due to industrial contamination. In this study, the concentrations of four heavy metals (cadmium, lead, mercury, and arsenic) in organs of two cyprinid fish and in water collected from three sections of the Kor River, Iran were determined using the inductively coupled plasma method. Pathological and hormonal changes due to metal contamination were also measured. The concentrations of heavy metals in tissue of fish from the middle sampling zone were significantly higher (p?<?0.05) than those from the other two sampling zones, whereas no significant differences (p?>?0.05) were detected between the two sexes and species. High levels of metals were found in the ovaries and testes; estradiol in females and progesterone and testosterone in males from the middle study site were significantly (p?<?0.05) lower than values from the other two sites. Pathological changes in blood cells, liver, and kidneys of fishes were significantly higher in highly polluted areas (middle sampling zone). These results show that industrial activities have polluted the river and that the maximum concentrations of Cd, Pb, and Hg were higher than the permissible levels for human consumption.