Biomonitoring of testate amoebae (protozoa) as toxic metals absorbed in aquatic bryophytes from the Hg-Tl mineralized area (China)

A new method has been developed for the determination of chemical oxygen demand (COD) in pulping effluent using chemometrics-assisted spectrophotometry. Two calibration models were established by inducing UV-visible spectroscopy (model 1) and derivative spectroscopy (model 2), combined with the chemometrics software Smica-P. Correlation coefficients of the two models are 0.9954 (model 1) and 0.9963 (model 2) when COD of samples is in the range of 0 to 405 mg/L. Sensitivities of the two models are 0.0061 (model 1) and 0.0056 (model 2) and method detection limits are 2.02?C2.45 mg/L (model 1) and 2.13?C2.51 mg/L (model 2). Validation experiment showed that the average standard deviation of model 2 was 1.11 and that of model 1 was 1.54. Similarly, average relative error of model 2 (4.25%) was lower than model 1 (5.00%), which indicated that the predictability of model 2 was better than that of model 1. Chemometrics-assisted spectrophotometry method did not need chemical reagents and digestion which were required in the conventional methods, and the testing time of the new method was significantly shorter than the conventional ones. The proposed method can be used to measure COD in pulping effluent as an environmentally friendly approach with satisfactory results.     

浙江近岸海域春季表层溶解氧饱和度分布及影响因素

根据2014年春季对浙江省近岸海域溶解氧的调查结果,结合现场的温度和盐度,得出溶解氧饱和度的平面分布,并在此基础上探讨了饱和度与温度、盐度、化学需氧量、浮游植物丰度之间的关系。结果显示,浙江省近岸海域溶解氧饱和度范围为92.1%~120%,均值为100%。总体呈西部沿岸低,东部外海高的平面分布趋势。溶解氧饱和度高值区与浮游植物丰度的高值区一致。低饱和区域化学需氧量含量基本高于1 mg/L。陆源径流和有机物质耗氧分解是沿岸低饱和区域主要控制因素,外海水和浮游植物光合作用是高饱和区域主要控制因素。径流和外海水对有机物质分解和浮游植物光合作用有一定的调控作用。     

Sensitive spectrophotometric methods for the assessment of nitrite in water sample

Two spectrophotometric methods have been developed for the determination of nitrite using dapsone (DAP) with alpha-naphthol and 4-amino-5-hydroxynapthalene-2,7-disulphonic acid monosodium salt (AHNDMS) as chromogenic reagents with maximum absorbance wavelength at 540 and 520 nm respectively. For the method that utilizes dapsone with alpha-naphthol (DAP-alpha-naphthol), the beer's law range is obeyed between 0.05-0.8 microg ml(-1) with molar absorptivity of 5.749 x 104 l mol(-1) cm(-1). The second method that uses dapsone with AHNDMS (DAP-AHNDMS), the beer's law is valid over the range 0.2-1.4 mug ml(-1) and molar absorptivity 2.44 x 104 l mol(-1) cm(-1). The common interfering ions in the analytical procedures have been studied. This proposed methods are reliable, reproducible and have been successfully applied to determine nitrite in various water sources of environmental interest.     

Performance of an electrochemical COD (chemical oxygen demand) sensor with an electrode-surface grinding unit

An electrochemical COD (chemical oxygen demand) sensor using an electrode-surface grinding unit was investigated. The electrolyzing (oxidizing) action of copper on an organic species was used as the basis of the COD measuring sensor. Using a simple three-electrode cell and a surface grinding unit, the organic species is activated by the catalytic action of copper and oxidized at a working electrode, poised at a positive potential. When synthetic wastewater was fed into the system, the measured Coulombic yields were found to be dependent on the COD of the synthetic wastewater. A linear correlation between the Coulombic yields and the COD of the synthetic wastewater was established (10-1000 mg L(-1)) when the electrode-surface grinding procedure was activated briefly at 8 h intervals. When various kinds of wastewater samples obtained from various sewage treatment plants were measured, linear correlations (r(2)> or = 0.92) between the measured EOD (electrochemical oxygen demand) value and COD of the samples were observed. At a practical wastewater treatment plant, the measurement system was successfully operated with high accuracy and good stability over 3 months. These experimental results show that the application of the measurement system would be a rapid and practical method for the determination of COD in water industries.     

Measurement of wastewater treatment efficiency by fluorescence and UV absorbance

The degree of chemical treatment in terms of removal of organic matter from different wastewaters has been investigated by employing potassium ferrate (K₂FeO₄) and ozone in various combinations. The study was performed in both the batch and the continuous flow systems. The treatment efficiency was determined through three different methods, i.e., chemical oxygen demand (COD), fluorescence and ultraviolet (UV) absorption. Fluorescence and UV absorption techniques were employed due to their specificity in measurement of humic substances, aromatic compounds and heterocyclic systems, whereas COD is a general parameter for the estimation of total organic matter. Fluorescence and UV absorbance values were correlated with respective COD values.Abdul Bari is with the Department of ChemistryShaukat Farooq is with the Department of Civil Engineering     

化学需氧量和总有机碳在水质在线监测中的比较

化学需氧量（COD）和总有机碳（TOC）是定量表示水体受有机物污染的2个重要代表性指标。传统的COD在线监测方法在监测有机污染物方面存在一定的挑战,系统比较了COD和TOC在线监测方法在特殊水质中的应用。结果显示：TOC对难氧化有机物的氧化效率高达98%,高氯离子和无机还原性离子对TOC测量误差影响分别约为10%和7%。TOC可更直接、更准确地反映出水体受有机物污染的情况,最后对TOC指标在水质在线监测中的推广应用提出建议。     

Solid phase extraction of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions with 1-(2-thiazolylazo)-2-naphthol loaded Amberlite XAD-1180

A new method for separation and preconcentration of trace amounts of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions in various matrices was proposed. The method is based on the adsorption and chelation of the metal ions on a column containing Amberlite XAD-1180 resin impregnated with 1-(2-thiazolylazo)-2-naphthol (TAN) reagent prior to their determination by flame atomic absorption spectrometry (FAAS). The effect of pH, type, concentration and volume of eluent, sample volume, flow rates of sample and elution solutions, and interfering ions have been investigated. The optimum pH for simultaneous retention of all the metal ions was 9. Eluent for quantitative elution was 20 ml of 2 mol l(-1) HNO(3). The optimum sample and eluent flow rates were found as 4 ml min(-1), and also sample volume was 500 ml, except for Mn (87% recovery). The sorption capacity of the resin was found to be 0.77, 0.41, 0.57, and 0.30 mg g(-1) for Cu(II), Ni(II), Cd(II), and Mn(II), respectively. The preconcentration factor of the method was 200 for Cu(II), 150 for Pb(II), 100 for Cd(II) and Ni(II), and 50 for Mn(II). The recovery values for all of the metal ions were > or = 95% and relative standard deviations (RSDs) were < or = 5.1%. The detection limit values were in the range of 0.03 and 1.19 microg l(-1). The accuracy of the method was confirmed by analysing the certified reference materials (TMDA 54.4 fortified lake water and GBW 07605 tea samples) and the recovery studies. This procedure was applied to the determination of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) in waste water and lake water samples.     

Optimization of pulp mill effluent treatment with catalytic adsorbent using orthogonal second-order (Box-Behnken) experimental design

Novel catalytic adsorbent (ruthenium on carbon) was employed for the treatment of pulp mill effluent in the presence of hydrogen peroxide. Mathematical model and optimization of the process regarding the most favorable COD (%), TOC (%) and color (%) removal rates was developed and performed with experimental design taking into account catalytic adsorption process kinetics. As the initial experimental design, 3(3-1) half-fractional factorial design (H-FFD) was accomplished at two levels to study the significance of the main effects, such as catalytic adsorbent (g l(-1)) and hydrogen peroxide (ppm) concentrations using the response surface methodology (RSM). Finally, a four factor-three coded level central composite design (CCD) with 28 runs was performed in order to fit a second-order polynomial model. Validation of the model was accomplished by different criteria including coefficient of determination and the corresponding analysis of variance. The achieved removal rates for TOC (up to 75%), COD (up to 73%) and color (up to 68%) were observed for the defined optimal conditions: 1g l(-1) of ruthenium on carbon, 7 ppm of hydrogen peroxide, pH = 4 and ambient temperature. The proposed method benefited significantly improved TOC, COD and color removal efficiency, regenerability and reusability of the catalytic adsorbent and unaltered initial pH of an effluent in comparison to traditional adsorption or oxidation processes.     

Cement for stabilisation of industrial residues containing heavy metals

A method aimed at decreasing the toxicity of heavy metals [namely, Zn(II) and Cr(III)] in real polluted residues by immobilisation has been developed. The residues were processed either with two cement-type stabilisers or lime. The cement-type stabilisers were Portland cement and Depocrete SM/2 at the self-generated pH (ca. 11) which afforded physical as well as chemical potential for the immobilisation of heavy metals. The other stabiliser, lime, reduced organic compounds, thus favouring the decrease of the chemical oxygen demand (COD) and endowing the residue with better mechanical properties for transport. After leaching the stabilised residues using the standard leaching test [Order 13/10/89, Boletín Oficial del Estado (BOE) 270 10/11/89], three ways for establishing the toxicity of the treated residues were used, namely: (1) the ecotoxicity test using Photobacterium phosphoreum (DIN 38 412); (2) determination of the concentration of heavy metals by atomic absorption spectrometry (AAS); (3) determination of the COD or oxygen required for complete chemical oxidation of a water sample. Portland cement (20%) blended with Depocrete SM/2 (3%) acted as an effective stabiliser for residues containing heavy metals as it increased the ecotoxicity index (EC50) by more than five times. Thus the heavy metal concentration in the leaching liquid was lowered to less than 0.1 mg l-1. The addition of 5% of lime afforded a residue easily transportable from the place of treatment to the landfill. The precision of the method was studied in terms of both repeatability and reproducibility. The values found with respect to EC50 and expressed as the relative standard deviation (RSD) were 1.6% and 5.1%, respectively.     

基于WASP 7模型的水质模拟应用——以淮沭新河东海段为例

应用WASP 7模型的EUTRO子模块对淮沭新河东海段的溶解氧(DO)和化学需氧量(COD)指标进行模拟研究,采用2014年与2015年的水文、水质数据进行模型参数率定,并以2016年1月—2017年9月的水质数据进行验证,验证结果为DO和COD的模拟值与实际值的相对误差分别能控制在15%和10%以内,线性回归分析结论显示相关系数R2均在0.9以上,表明两者的吻合度较高。     

Airborne endotoxin in woodworking (joinery) shops

Symptoms such as shortness of breath and cough have been noted in woodworking facilities even where wood dust itself is well-controlled. Suspicion has fallen on other possible contaminants in the workplace atmosphere, including bacterial endotoxin. A few studies have indicated potentially high endotoxin exposure with exposure to fresh wood in sawmills and in the production of fiberboard and chipboard, but fewer studies have been carried out on exposure to endotoxin in dry wood work, for example in joineries. A study of the endotoxin content of airborne wood dust samples from US woodworking facilities is presented, from the re-analysis of samples which previously had been taken to establish mass collection relationships between the IOM sampler, the closed-face 37 mm plastic cassette (CFC) sampler and the Button sampler. Endotoxin was strongly correlated with total dust, but the endotoxin content of a few fresh wood samples was found to be up to ten times higher per unit of wood dust than for dried-wood samples, and this difference was significant. No long-term time-weighted average sample exceeded the recommended limit value of 50 EU m(-3) (EU, endotoxin units)used in the Netherlands, although a number of the IOM samples came close (seven samples or 44% exceeded 20 EU m(-3)) and one short-term (48 minute) sample registered a high value of 73 EU m(-3). The geometric mean concentration from the IOM samples (11 EU m(-3)) is within the range of geometric means found from Australian joineries (3.7-60, combined: 24 EU m(-3)). In contrast, the corresponding values from the CFC (3.6 EU m(-3)), and the Button sampler (2.1 EU m(-3)) were much lower and no samples exceeded 20 EU m(-3). Endotoxin is likely only to be a significant problem in working with dried woods when associated with very high dust levels, where the wood dust itself is likely to be a cause for concern. The results from the few samples in this study where fresh wood was being worked were similar to results from other studies involving fresh woods. The agreement between these studies is encouraging given the difficulties of endotoxin analysis and the wide variation often expected between different laboratories.     

Determination of N-acetyl-S-(N-methylcarbamoyl)cysteine (AMCC) in the general population using gas chromatography-mass spectrometry

Carbamoylation of glutathione, peptides and DNA is thought to be one of the most important reactions occurring in an organism after exposure to nitrosoureas, methylformamides or isocyanates. The carcinogenic effects of carbamoylation are not yet fully clarified. Although carbamoylation is known to occur after occupational exposure, it has never been reported in the general population. To clarify the situation, we investigated the levels of N-acetyl-S-(N-methylcarbamoyl)cysteine (AMCC) in urine samples from persons without occupational exposure using a sensitive and specific method (gas chromatography-mass spectrometry, GC-MS). AMCC is the degradation product of N-methylcarbamoylated glutathione. The clean-up procedure of urine samples includes two liquid-liquid extraction steps and solid phase extraction using a cation-exchange resin to separate AMCC from other urinary components. N,N-Dimethylpropionic acid amide (DMPA) is used as internal standard. During the preparation of the samples, AMCC is converted to ethyl-N-methylcarbamate (EMC) in the presence of anhydrous potassium carbonate (K2CO3) and ethanol. The reliability and accuracy of this method have been proven in detail. The relative standard deviation for the within-series imprecision for three different concentrations was determined to be between 10.9% and 14.3%, while the relative standard deviation for the between-day imprecision was between 11.3% and 14.8%. The mean recovery for AMCC was determined to be between 79.2% and 85.6%. The limit of detection for the simultaneous measurement of two fragment masses was 30 micrograms L-1. Using this GC-MS method, we analysed urine samples from 42 individuals of the general population in order to determine their urinary excretion of AMCC. It was identified in 40 samples. The mean concentration was 40 micrograms L-1. AMCC can be formed in two ways. The first possibility is the dietary intake of isothiocyanates, especially methyl isothiocyanate, which is a component of wine and cruciferous vegetables (such as cabbage, turnips and cress). During the metabolism of isothiocyanates in humans, the sulfur is partly exchanged for oxygen resulting in the formation of the corresponding isocyanate derivatives. The other possibility is the physiological formation of AMCC. In humans, this may occur via a two step process: carbamoylation and methylation, or vice versa. However, as AMCC was identified in about 95% of urine samples, and the standard deviation for the level of AMCC excreted was low, physiological formation seems to be the more probable pathway.     

A rapid extractive spectrophotometric determination of copper(II) in environmental samples, alloys, complexes and pharmaceutical samples using 4-N,N(dimethyl)amino]benzaldehyde thiosemicarbazone

Composite samples of septage discharging at the Khirbit As-Samra municipal wastewater treatment plant were analyzed during the period from February to the end of October 2007. Septage showed difference in concentrations of pollutants between summer and winter. The average total chemical oxygen demand (COD) of 6,425 mg/L during summer was 2.16 times greater than that in winter, which is 2,969 mg/L. The total biochemical oxygen demand (5 d) represented 45% of total COD in both winter and summer. Anaerobic biodegradability was 75% after 81 d of digestion at 35°C with a biodegradation rate constant (k) of 0.024 d^???1, which was lower compared with 0.103 d^???1 calculated for wastewater with domestic origin in Jordan. Aerobic biodegradability for septage was 48%??COD basis??after 7 d of digestion at 35°C. The lower anaerobic biodegradation rate of septage compared with that of raw wastewater of domestic origin suggested that septage could have a negative effect on the performance of a domestic wastewater treatment plant if septage discharges are not taken into account in the original design of the treatment plant.     

Smart现场分析仪测定化学需氧量、氨氮

对Ｓｍａｒｔ现场分析仪测定化学需氧量、氨氮作了简单地介绍，并用实际水样与化学法进行了对比试验。测定结果表明，两者之间相对误差均在１１％以内，较为一致。仪器体积小、携带方便，操作简单、快捷，试剂消耗少，可在现场从事应急监测。     

Total organic carbon analysis as a precursor to disinfection byproducts in potable water: oxidation technique considerations

In recent years, an increasing number of regulations and methodologies have begun to utilize total organic carbon (TOC) analysis for monitoring microbial contamination and/or disinfectant byproduct (DBP) precursors. This paper highlights some analytical differences and similarities between the two widely used TOC oxidation techniques: UV persulfate and high temperature combustion (HTC). Previous papers have come to different and sometimes contradictory conclusions on this subject. However, these studies either compared instruments with significantly different flow paths or TOC systems from different eras. Unlike previous studies, this paper compares two modern TOC analyzers with nearly identical flow paths for sample recovery, detection limits, and analysis of real world samples. On average, both persulfate and HTC oxidation yielded good recoveries for 10 hard to oxidize compounds and potable water samples from 5 different locations across the USA. In general, persulfate yielded more precise results because of its lower background response relative to sample response while HTC gave slightly higher results (roughly 2% to 3%) for surface water samples.     

我国洗衣粉消费形成的COD总量测

根据水质COD重铬酸钾法，实测了市场上5种常见品牌洗衣粉的COD负荷值，得到其平均值为0．328（w／w）（绝干洗衣粉）。由我国使用量计算得到2005年洗衣粉形成的COD总量为88．87×10^4t，这相当于当年全国工业和生活COD排放总量的6．3％，全国生活COD排放总量的10．3％，2005年我国洗衣粉消费过程COD产污系数为1．86g／（d·人），需要对洗衣粉消费形成的COD总量水平予以必要的关注。     

Speciation of As(III) and As(V) in water and sediment using reverse-phase ion-pair high-performance liquid chromatography-neutron activation analysis (HPLC-NAA)

Total As content and the As species distribution in water and sediments from the Kwabrafo stream, a major water body draining the Obuasi gold mining community in southwestern Ghana, have been investigated. Total As content was determined by instrumental neutron activation analysis (INAA). Ion-pair reverse phase high-performance liquid chromatography-neutron activation analysis (HPLC-NAA) was used for speciation of As species. Solid phase extraction with phosphate buffer was used to extract soluble As species from lyophilized sediment. The mass balance after phosphate extraction of soluble As species in sediment varied from 89 to 96 %. Compositionally appropriate reference material International Atomic Energy Agency (IAEA)-Lake Sediment (SL)-1 was used to check the validity of INAA method for total As determination. The measured values are in good agreement with the IAEA recommended value and also within the 95 % confidence interval. The accuracy of the measurement in terms of relative deviation from the IAEA recommended value was ±0.83 %. “In-house” prepared As(III) and As(V) standards were used to validate the HPLC-INAA method used for the As species determination. Total As concentration in the water samples ranged from 1.15 to 9.20 mg/L. As(III) species in water varied from 0.13 to 0.7 mg/L, while As(V) species varied from 0.79 to 3.85 mg/L. Total As content in sediment ranged from 2,134 to 3,596 mg/kg dry mass. The levels of As(III) and As(V) species in the sediment ranges from 138 to 506 mg/kg dry mass and 156 to 385 mg/kg dry mass, respectively.     

Analysis of tropospheric ozone concentration on a Western Mediterranean site: Castellon (Spain)

Ozone dynamics in our study area (Castellon, Spain) is both strongly bound to the mesoscale circulations that develop under the effect of high insolation (especially in summer) and conditioned by the morphological characteristics of the Western Mediterranean Basin. In this work we present a preliminary analysis of ozone time series on five locations in Castellon for the period 1997–2003. We study their temporal and spatial variations at different scales: daily, weekly, seasonally and interannually. Because both the O₃ concentration and its temporal variation depend on the topographic location of the observing station, they can show large differences within tens of kilometer. We also contrast the variation in the ozone concentration with the variations found for meteorological variables such as radiation, temperature, relative humidity and recirculation of the air mass. The link between elevated ozone concentrations and high values of the recirculation factor (r=0.7–0.9) shown the importance of recirculating flows on the local air pollution episodes.     

Development of a new automated clean-up system for the simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (dl-PCB) in flue gas emissions by GPC-SPE

A comprehensive clean-up method for quantitative analysis of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples was developed. Since the chemical nature and toxicity of planar PCBs are similar to those of PCDD/Fs, dioxin-like PCBs and PCDD/Fs are often surveyed together in their exposure assessments. The development of a method for the simultaneous analysis of PCBs and PCDD/Fs in environmental samples is invaluable. The automated clean-up system evaluated in this work consists of three additional steps after traditional extraction: the chromatography on gel permeation (GPC), the concentration of the solvent through the use of an in-line evaporation module and the further purification and separation of PCDDs/Fs and dl-PCBs on an alumina cartridge in the 'SPE module'. In this work, three fly ash samples from an interlaboratory study with different PCDD/F and PCB levels were Soxhlet-extracted and then cleaned up using an automated system. PCDD/Fs and PCBs were determined using isotope dilution and high resolution gas chromatography/high resolution mass spectrometry. The determined values of 17 PCDD/Fs were consistent with the certified values and the relative standard deviations (RSDs) of the determined values were less than 20%. The recoveries of (13)C labeled PCDD/Fs and planar PCBs, and their RSDs were within the ranges specified in EPA1613 and 1668a methods, respectively. An accurate and reliable method was successfully developed and can be used in the simultaneous analysis of PCDD/Fs and planar PCBs in environmental samples.