Evaluation of the presence of drugs of abuse in tap waters

A total of seventy samples of drinking water were tested for non-controlled and illicit drugs. Of these, 43 were from Spanish cities, 15 from seven other European countries, three from Japan and nine from seven different Latin American countries. The most frequently detected compounds were caffeine, nicotine, cotinine, cocaine and its metabolite benzoylecgonine, methadone and its metabolite EDDP. The mean concentrations of non-controlled drugs were: for caffeine 50 and 19 ng L⁻¹, in Spanish and worldwide drinking water respectively and for nicotine 13 and 19 ng L⁻¹. Illicit drugs were sparsely present and usually at ultratrace level (<1 ng L⁻¹). For example, cocaine has mean values of 0.4 (Spain) and 0.3 ng L⁻¹ (worldwide), whereas for benzoylecgonine, these mean values were 0.4 and 1.8 ng L⁻¹, respectively. Higher concentrations of benzoylecgonine were found in Latin American samples (up to 15 ng L⁻¹). No opiates were identified in any sample but the presence of methadone and EDDP was frequently detected. Total mean values for EDDP were 0.4 ng L⁻¹ (Spain) and 0.3 ng L⁻¹ (worldwide). Very few samples tested positive for amphetamines, in line with the reactivity of chlorine with these compounds. No cannabinoids, LSD, ketamine, fentanyl and PCP were detected.     

Kinetics of oxidation of methylhydrazines in water. Factors controlling the formation of 1,1-dimethylnitrosamine

The kinetics of oxidation of methylhydrazine ($\text{MMH}$) and 1,1-dimethylhydrazine ($\text{UDMH}$) by dissolved oxygen in water has been measured at various acidities as a function of catalyst (cupric ion) concentration. In dilute solutions the oxidation occurs through a cupric ion catalyzed process as well as by an uncatalyzed step. The extent of formation of nitrosodimethylamine ($\text{NDMA}$) depends upon the initial $\text{UDMH}$ concentration. In dilute solutions $\text{NDMA}$ is not formed, but in more concentrated solutions, $\text{NDMA}$ formation increases with increasing $\text{UDMH}$ content, reaches a maximum at 60–80% $\text{UDMH}$ (by volume) and then decreases. The $\text{NDMA}$ yield appears to approximately parallel the viscosity of the medium, and it is speculated that the factors which control viscosity may also be responsible for governing $\text{NDMA}$ formation.     

Low doses of chlorpyrifos interfere with spermatogenesis of rats through reduction of sex hormones

Use of pesticides results in indirect effects on human health. We aimed to evaluate implications of toxicological effects of subchronic chlorpyrifos exposure on reproductive function in male rats. A total of 48 adult Wistar male rats were separated into four groups (n = 12). Animals were gavaged with 2.5 mg/kg (T1), 5 mg/kg (T2), or 10 mg/kg (T3) body weight of chlorpyrifos (CPF) or distilled water (control) daily for 30 days. Organ weights, epididymal sperm parameters, DNA integrity, sex hormonal (FHS and LH) levels, and alanine aminotransferase (ALT), aspartate aminotransferase (AST), gamma-glutamyl transferase (GGT), and creatinine concentrations were determined on day 31. Another two sets of (four groups/set; n = 10) animals were orally treated with the same doses of CPF, control animal groups were treated with distilled water only for 30 days, and fertility indices and blood plasma acetylcholine esterase (AchE) were determined on day 31. Exposure to CPF resulted in a significant (p < 0.05) decrease in weights of testis and epididymis. An increase in liver weight resulted in reduced sperm counts and sperm motility and an increase in sperm abnormalities. Significant reduction in serum testosterone (p < 0.01), luteinizing hormone (p < 0.05), and follicular stimulating hormone (p < 0.05) levels was evident in animals treated with the highest dose. A significant decrease in the number of viable implantation sites and pups was observed in female rats mated with the T3 (p < 0.01) and T2 (p < 0.05) males. The ALT, AST, GGT, and creatinine contents were significantly increased (p < 0.05 and p < 0.01, respectively) on CPF exposure. A significant (p < 0.01) reduction in blood plasma AchE enzyme was observed with the highest dose. Our results demonstrated that prolonged exposure of CPF induces spermatogenesis damage, possibly through interference with sex hormones and AchE enzyme resulting in reduction of fertility. Therefore, awareness programs on handling CPF (pesticides) to enhance safety warrant minimization of its hazards.     

Measurement of vapour pressures of Fenitrothion and Matacil

Vapour pressures of Fenitrothion and Matacil were measured using a gas saturation method. Polyurethane foam was used to trap the volatilized materials from sand and glass surfaces, and Porapak Q for trapping materials volatilized from leaf surfaces. The vapour pressures (VP) were linearly related to the reciprocal temperature by the equation: $\text{Log (VP)}\text{= 6.3362 ? (}\text{3197.8}\text{T}\text{)}$ for a sand incorporated with Fenitrothion and $\text{Log (VP)}\text{= 8.8316 ? (}\text{4021.4}\text{T}\text{)}$ for a sand incorporated with Matacil. The greatest vapour loss rates were from sand incorporated with fenitrothion, followed by vapour loss rates from glass surfaces; the least vapour loss rate was from leaf surfaces.     

Effects of multigenerational exposures of D. magna to environmentally relevant concentrations of pentachlorophenol

The re-emergence of schistosomiasis has given rise to ubiquitous concentrations of the primary control agent pentachlorophenol (PCP) in the environment, especially in the surface waters of China. In this study, the effects of environmentally relevant concentrations of PCP, namely, 0.0002, 0.002, 0.02, 0.2, and 2 μmol/L on survival, age at first reproduction, fecundity, length of mothers, and number of molts of Daphnia magna were studied over three generations. The survival of D. magna exposed to 2 μmol/L was significantly affected in the three generations. Toxic effects were enhanced in later generations. Age at first reproduction of F ₁ and F ₂ D. magna was significantly slower than that of the controls. The total number of offspring per female exposed to concentrations of 0.002 μmol/L or greater was less (23.5 to 67.6, 9.4 to 73.7, and 3.6 to 83.7 %) than that of the controls in the F ₀, F ₁, and F ₂ generations, respectively. The body length of mothers significantly decreased (4.7 to 6.8, 9.6 to 15.1, and 13.3 to 23.2 %) after exposure to 0.002 μmol/L or greater than those of unexposed individuals in the F ₀, F ₁, and F ₂ generations, respectively. Dose–response relationships between concentrations of PCP and length and number of molts of D. magna were observed in the F ₀ to F ₂ generations. PCP concentrations on the surface waters of China caused adverse effects to D. magna, which increased over successive generations. Significant effects were observed in the third generation. The multigenerational studies were more sensitive than the single-generation experiments. Thus, multigenerational exposure may be more predictive of chronic exposure under field conditions.     

Laboratory studies of the impact of aerosol composition on the heterogeneous oxidation of 1-propanol

The effects of (NH₄)₂SO₄, NH₄NO₃, NaCl, NH₄Cl, and Na₂SO₄ aerosols on the kinetics of 1-propanol oxidation in the presence of the hydroxyl radical have been investigated using the relative rate technique. p-Xylene was used as a reference compound. Two different aerosol concentrations that are typical of polluted urban conditions were tested. The total surface areas of aerosols were 1400 (condition I) and 3400 μm² cm⁻³ (condition II). Results indicate that aerosols promote the oxidation of 1-propanol, and the extents of the promoting effects depend on the aerosol composition and concentration. Increases in the relative rates of the 1-propanol/OH reaction vs. the p-xylene/OH reaction were only observed for (NH₄)₂SO₄ aerosol conditions I and II, NH₄NO₃ aerosol condition II, and NH₄Cl aerosol condition II. These results indicate that NH₄⁺ is the species promoting the oxidation of 1-propanol, and suggests the possibility of a strong interaction between NH₄⁺ and 1-propanol that can change the activation energy of the initial OH attack. These results have profound implications on the use of air quality models for the assessment of air pollution control strategies.     

巢湖入湖河流沉积物中有机磷的形态分级研究简

为识别巢湖流域污染物的特征、来源及其沉积物有机磷各形态分布与富营养化的关系，测定了7条巢湖入湖河流沉积物中有机磷各形态的含量，分析不同污染类型入湖河流沉积物中有机磷各形态分布的差异及与其他因素间的相关性。研究发现，不同污染类型入湖河流沉积物中水土保持控制型河流沉积物中有机磷各组分的相对含量顺序为残渣态P_o >富里酸-P_o >HCl-P_o >胡敏酸-P_o >NaHCO₃-P_o，平均的相对比例为7.5：3.1：1.9：1.5：1.0，而城市污染控制型和面源污染控制型河流沉积物中有机磷各组分的相对含量顺序恰好相同，面源污染控制型河流沉积物P_o各形态含量低于城市污染控制型和水土保持控制型河流。中活性P_o和OM、TP、P_i、P_o、TN、NaHCO₃-P_i、NaOH-P_i呈正相关，非活性P_o与P_o、NaOH-P_i呈显著正相关关系，反映了中活性P_o很容易转化为生物可利用磷和非活性P_o，且非活性P_o仍然具有潜在的生物活性。     

Estimation of dry deposition of atmospheric nitrogen to coastal waters of de la Plata River in front of Buenos Aires city

The deposition of atmospheric nitrogen (N) to surface waters of de la Plata River downwind of Buenos Aires city has been estimated using atmospheric dispersion-deposition models. The CALPUFF model has been applied to point source emissions and the DAUMOD-RD model has been developed to evaluate the area source emission contributions. Annual N dry deposition is 31,763 kg-N yr⁻¹ (≈ 18 kg-N km⁻² yr⁻¹). Nitrogen dioxide contribution to this value is 54% and nitric acid contribution is 46%. The maximum monthly N dry deposition fluxes vary between 7 kg-N km⁻² month⁻¹ (in February) and 13 kg-N km⁻² month⁻¹ (in December).     

A laboratory study of the effect of NO2 on the atmospheric corrosion of zinc

Studies on the effect of NO_x on zinc corrosion are scarce and their results are variable and at times seemingly contradictory. This paper reports laboratory tests involving the dry deposition on zinc surfaces of 800 μg m⁻³ NO₂, alone and in combination with 800 μg m⁻³ SO₂, at temperatures of 35 and 25 °C and relative humidities of 90% and 70%. From the gravimetric results obtained and from the characterisation of the corrosion products by optical microscopy, scanning electron microscopy (SEM/EDX), grazing incidence X-ray diffraction (GIXD) and X-ray photoelectron spectroscopy (XPS), it has been verified that the corrosive action of NO₂ alone is negligible compared with SO₂. However, an accelerating effect has been observed when NO₂ acts in conjunction with SO₂ at 25 °C and 90% RH. At 35 °C and 90% RH, the accelerating effect is smaller, and at low relative humidities (70%), the synergistic effect is only slight, which suggests it may be favoured by the presence of moisture. In those cases where an accelerating effect has been observed, a greater proportion of sulphate ions has been found in the corrosion products, and nitrogen compounds have not been detected, indicating that NO₂ participates indirectly as a catalyst of the oxidation of SO₂ to sulphate.     

Nitrification of centrate from dewatering of anaerobically digested sludge

Nitrification of anaerobically digested sludge centrate was studied in bench-scale suspended growth and fixed film enhanced suspended growth systems at temperatures of 10.5-28.5°C and pH values of 6.0-9.1. Nitrification followed zero-order kinetics in both systems, and ammonia removals in excess of 99% were observed. The temperature dependency of the suspended growth nitrification rate observed under not fully acclimated biomass conditions at pH between 6.8 and 8.5, was expressed as k_T = k₂₀θ^T-20where k₂₀ and θ were found to be 0.34 mg NH₃-N/MLVSS-d and 1.033, respectively. The nitrification rate in the fixed film enhanced suspended growth system involving styrofoam pads ranged from 0.11 to 0.13 mg NH₃-N/mg MLVSS-d at temperatures of 21.5-25°C and pH values of 7.8-8.6. The process contained suspended solids in the range of 10-20 mg/l.     

Effects of nanoparticles in species of aquaculture interest

Recently, it was observed that there is an increasing application of nanoparticles (NPs) in aquaculture. Manufacturers are trying to use nano-based tools to remove the barriers about waterborne food, growth, reproduction, and culturing of species, their health, and water treatment in order to increase aquaculture production rates, being the safe-by-design approach still unapplied. We reviewed the applications of NPs in aquaculture evidencing that the way NPs are applied can be very different: some are direclty added to feed, other to water media or in aquaculture facilities. Traditional toxicity data cannot be easily used to infer on aquaculture mainly considering short-term exposure scenarios, underestimating the potential exposure of aquacultured species. The main outputs are (i) biological models are not recurrent, and in the case, testing protocols are frequently different; (ii) most data derived from toxicity studies are not specifically designed on aquaculture needs, thus contact time, exposure concentrations, and other ancillary conditions do not meet the required standard for aquaculture; (iii) short-term exposure periods are investigated mainly on species of indirect aquaculture interest, while shrimp and fish as final consumers in aquaculture plants are underinvestigated (scarce or unknown data on trophic chain transfer of NPs): little information is available about the amount of NPs accumulated within marketed organisms; (iv) how NPs present in the packaging of aquacultured products can affect their quality remained substantially unexplored. NPs in aquaculture are a challenging topic that must be developed in the near future to assure human health and environmental safety.

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Graphical abstract ?

     

Fenton氧化法对磺胺类抗生素的降解动力学

采用Fenton氧化法同时降解水溶液中磺胺吡啶(SPY)、磺胺二甲基嘧啶(SMZ)和磺胺甲噁唑(SMX)。系统考查了初始H2O2浓度、Fe2+浓度、pH对3种磺胺类抗生素降解性能的影响。结果表明,3种磺胺抗生素被完全降解的最佳Fenton氧化条件是:H2O2浓度为2.0 mmol/L,Fe2+浓度为0.10 mmol/L,pH为3.0~3.5,反应时间为20 min。Fenton试剂对3种磺胺类抗生素的降解符合一级反应动力学,速度常数为0.0318~0.2002 min-1。     

Comparison of methods for evaluation of activity of photocatalytic films

Objective

This work aims to investigate the correlation between the photocatalytic activity determined by methylene blue bleaching (DIN 52980), stearic acid degradation, and degradation of acetone in gas phase.

Method

The photocatalytic TiO₂ coatings included in this investigation ranged from thin commercially available coatings (Activ^TM and BioClean^TM) and ready to use suspensions (Nano-X PK1245) to lab-produced PVD and sol?Cgel coatings. XRD analysis of the photocatalytic coatings showed that all the coatings consisted of nanocrystalline anatase, although the thickness and porosity varied considerably.

Results

The study showed that the reproducibility of the activity measurements was good. However, more importantly, the investigation showed that there is a good correlation between the activities determined by the different methods even though the characteristics of the photocatalytic coatings and the organic probe molecules varied considerably.

Conclusion

The overall findings of this work suggest that there is a good correlation between the investigated methods. These results are promising for the future work concerning standardization of methods for determination of the activity of photocatalytic films.     

电解质种类对电催化氧化降解苯酚的影响

研究了不同电解质对有机物电催化氧化性能的影响。以高温热解法制备了Ti/SnO2+Sb2O3阳极,用SEM和XRD对电极结构进行了表征。以苯酚为目标有机物,考察了Na2SO4、NaCl和NaNO33种不同电解质对苯酚降解效果的影响。用循环伏安法研究了苯酚在不同支持电解质条件下的电化学行为。采用碘量法测定了在不同电解质溶液中氧化性物质的生成量。研究结果表明,电极的活性涂层主要由SnO2和微量的Sb2O3组成,均匀完整地覆盖住了Ti基体表面。以NaCl为支持电解质时苯酚降解效果明显优于用Na2SO4、NaNO3为支持电解质,并且苯酚的降解主要以电极表面电化学生成的HClO和ClO-的间接化学氧化为主。以Na2SO4为支持电解质时有利于降低和稳定槽电压。在3种电解质条件下,苯酚的降解均遵循一级反应动力学规律。在降解过程中NaCl溶液中生成的氧化性物质浓度最大,且随降解时间延长逐渐增大。     

FT-IR product study of the OH-initiated oxidation of DMS in the presence of NOx

The influence of NO_x (NO+NO₂) concentrations on the product distribution of the OH-initiated oxidation of DMS has been studied at room temperature using total NO_x concentrations varying from 0 to ∼1800 ppbv (30–600 ppbv NO₂ and 140–1760 ppbv NO). Clear trends in the formation yields of the products SO₂, COS, MSA, MTF (methyl thiolformate), MSPN (methanesulphonyl peroxynitrate), DMSO and DMSO₂ have been observed with variation in NO_x. The presence of low levels of NO reduces the yields of both MTF and COS to zero. The formation yields of MSA and DMSO₂ increase with increasing NO_x concentration, whereas the yields of DMSO and SO₂ decrease. The following approximate changes in the yield, not corrected for possible loss processes, have been measured for variation of NO_x between 0 and ∼1800 ppbv: DMSO decreases from 20 to 3%S; DMSO₂ increases from 3 to 15%S, SO₂ decreases from 70 to 30%S and MSA increases from 4 to 17%S. Under the experiments conditions NO_x levels of several tens of ppbv are required before a perceptible change is observed in the MSA yield. If applicable to the atmosphere such a situation is only likely to be observed near coastal areas affected by pollution. MSPN (CH₃SO₂O₂NO₂) is observed as an oxidation product in the presence of NO₂ even at low levels (e.g. 60 ppbv). Its possible role as a NO_x reservoir in the troposphere is considered.     

Formation of toxic species and precursors of PCDD/F in thermal decomposition of alpha-cypermethrin

This article examines the thermal decomposition of alpha-cypermethrin, one of the most common pyrethroid pesticides. The objective was to identify its decomposition pathways and to gain an understanding into the formation of toxic species in the environment, including those that may behave in combustion systems, especially in fires in the environment, as precursors for PCDD/F (polychlorinated dibenzo-p-dioxins and dibenzofurans). The experiments were conducted under non-oxidative conditions using a tubular reactor housed in a three-zone heating furnace and operated with a dilute stream of alpha-cypermethrin in 99.999% nitrogen. The condensable products were identified and quantitated, after being collected in a cold solvent trap and in an activated charcoal cartridge. The study revealed the formation of pollutants including precursors of toxic PCDD/F such as diphenyl ether and phenol. It was also found that the decomposition of alpha-cypermethrin involved parallel pathways of an unusual vinylcyclopropane rearrangement-cum-aromatisation reaction transforming alpha-cypermethrin and a rupture of the C(O)OC(CN) linkage. The former is similar to that occurring in the decomposition of permethrin pesticide, whereas the latter constitutes a newly discovered channel for the formation of pollutants. Density functional theory (DFT) calculations allowed us to attribute the occurrence of the second pathway to the effect of the cyanide group in significantly weakening the OC bond.