Evidence for covalently bonded chlorine–fullerene formed by ozonation and chlorination at room temperature

This article reports for the first time that fullerene (nC₆₀) can form chlorinated disinfection by-products in aqueous systems at ambient temperature. The ability of nC₆₀ to form colloidal suspensions in aqueous media increases the chance that these particles will migrate in the environment and then in drinking water supply systems. Since nC₆₀ is not completely removed by conventional water treatment, any residual nC₆₀ is likely to be oxidized during disinfection process. While the ozonation of nC₆₀ has been studied, little is known about the reaction between nC₆₀ and chlorine. To address this issue, we subjected aqueous nC₆₀ suspensions to chlorination and sequential ozonation/chlorination at ozone dosages of 4.5, 10, 15 and 24 mg O₃/mg nC₆₀. The morphology and physicochemical properties of oxidized nC₆₀ aggregates were evaluated by scanning electron microscopy, transmission electron microscopy, UV–visible absorption spectroscopy and X-ray photoelectron spectroscopy (XPS). We found that while the particles in the as-prepared nC₆₀ were predominantly spheres, the ozonation of nC₆₀ resulted in the formation of irregularly shaped aggregates. The concentration of atomic carbon found by XPS in the nC₆₀ samples decreased from 92 % for the as-prepared nC₆₀ to 50 % for the aggregates ozonated at 24 mg O₃/mg nC₆₀ and then chlorinated at 68 mg Cl₂/L and allowed to react for 100 min. The presence of Cl atoms covalently bonded to C atoms was confirmed by XPS peaks corresponding to a binding energy (E _b) of 200.1–202.4 eV. This demonstrates the need to better assess and monitor the formation of potentially toxic chlorinated disinfection by-products from carbon nanomaterials during water treatment.     

ELISA determination of Aflatoxin M1 in milk and dairy products in Pakistan

A highly sensitive competitive ELISA was standardized to determine aflatoxin M₁ (AFM₁) in milk and dairy samples randomly collected from Faisalabad city, using Riedel-de-Haen, Aflatoxin M₁ ELISA Systems, (Art–No. 45169). Standards of 5, 10, 25, 50, and 100 ng L^?1 AFM₁ in sample/standard buffer were used in optimizing anti-AFM₁ antibodies and peroxidase–AFM₁ conjugate. Linear standard curve showed increase in concentration (log C) accompanied by decrease in maximal absorbance (%B/B₀) values (%B/B₀ = 124.3 ? 45.0 log C) with highly significant negative correlation (?0.973). The middle of the test (50% B/B₀) was at 30 ng L^?1 with 6.7 ng L^?1 the lowest detection limit (90% B/B₀). Duplicate analysis of 41 samples showed AFM₁ levels below EC permissible limits (50 ng L^?1) with maximums of 40, 13, and 7.4 ng L^?1 in milk, yogurt and butter, respectively. However, possibility of exceeding limits cannot be excluded, and demands regular monitoring.     

Oxidative stress and genotoxicity of 1-methyl-3-octylimidazolium chloride on loach (Misgurnus anguillicaudatus)

This study was a preliminary step to evaluate the acute toxicity of 1-methyl-3-octylimidazolium chloride ([C₈mim]Cl) on loach (Misgurnus anguillicaudatus) by determining the effects on hepatic antioxidant enzyme activities and by the comet assay. The results showed that [C₈mim]Cl had acute toxicity at concentrations above 20 mg L^?1, inducing oxidative stress and genotoxicity on fish liver cells. In respect to enzyme activities, [C₈mim]Cl induced changes in the activities of superoxide dismutase, catalase, and glutathione content the livers of fish exposed at 20–80 mg L^?1. [C₈mim]Cl at the same exposure level caused a remarkable increase in malondialdehyde level. The comet assay indicated that [C₈mim]Cl at 20–80 mg L^?1 induced genotoxicity in liver cells. With increased exposure concentration and time, the two comet parameters trailing rate and tail moment were significantly increased, with significant differences (P < 0.05) observed between control group and each treatment group. The present study shows that ionic liquids can be a threat to the health of aquatic organism when accidentally released to aquatic ecosystems.     

Assessment of toxicity of two nitroaromatic compounds in the freshwater fish Cyprinus carpio

This study was conducted to evaluate the toxicological response of p-nitrotoluene and p-nitroaniline to the key fish species, Cyprinus carpio. A freshwater fish bioassay based on the 96 h LC ₅₀ was used to estimate the single and joint toxicity of the two chemicals. The toxicity of p-nitrotoluene was greater than that of p-nitroaniline based on 96 h LC ₅₀ values of 40.74 mg·L^?1 and 48.99 mg·L^?1, respectively. Both compounds had moderate toxicity toward Cyprinus carpio, and this toxicity increased with the exposure duration and concentration. Binary mixtures of the compounds were more toxic than the individual compounds at 96 h, and they acted upon partial addition. When the exposure time was longer, the toxicity increased for mixtures of compounds with the same concentration or toxicity. The results of this study suggest that exposure to a combination of these chemicals would result in a higher environmental risk in aquatic systems than exposure to either compound alone. Further research is needed to investigate the combined effects and sublethal toxicity of p-nitrotoluene and p-nitroaniline, since they are both still used in China.     

含氯苯酚类化合物结构表征与毒性预测

将有机化合物中的不同非氢原子及非氢原子之间的关系参数化得到新的结构描述符，运用该描述符对部分含氯苯酚类化合物分子结构进行了参数化表征。采用偏最小二乘回归(PLS)方法构建了化合物结构与毒性(-lgIC₅₀)之间的关系模型，模型的建模相关系数(R²)为0.948，“留一法”交互检验的相关系数(Q²)为0.922，标准偏差(SD)为0.184。结果表明结构描述符能较好地表征化合物分子结构特征，所建模型稳定性好、预测能力强，对于酚类化合物QSAR研究具有一定的参考价值。     

Susceptibility of Eucalyptus globulus to Mnesampela privata defoliation in relation to a specific foliar wax compound

Summary. Increased abundance of several aliphatic benzyl and phenylethyl alkanoates were previously associated with reduced defoliation of Eucalyptus globulus Labill. by the autumn gum moth (Mnesampela privata Guenée) in two clonally replicated F₂ families. We examine the robustness of this association by comparing the abundance of the implicated foliar wax compounds with defoliation levels in three plantation sites and a genetics trial in northern Tasmania. At all locations, the aliphatic alkanoate, benzyl n-tetracosanoate (C₂₄), was found in significantly higher abundance in the foliar wax of E. globulus trees that had displayed low M. privata damage (designated resistant) compared to trees that had displayed high damage (designated susceptible). Further, when sites were combined, benzyl n-tetracosanoate (C₂₄) accounted for 16 % of variation in field defoliation. Field defoliation was also positively correlated to M. privata oviposition both in the field and on foliage sprigs in a cage. In the cage bioassay, oviposition accounted for 20 % of variation in field defoliation making it a better predictor of tree defoliation in the field than either field oviposition, which accounted for 9 % of variation, or screening foliage for the abundance of benzyl n-tetracosanoate (C₂₄). Despite both benzyl n-tetracosanoate (C₂₄) and oviposition being related to field defoliation, there was no statistically significant relationship between the abundance of benzyl n-tetracosanoate (C₂₄) and oviposition in the field or cage bioassay. Further work is therefore required to determine if increased levels of this compound in the foliar wax operates as a direct deterrent to M. privataoviposition.     

Levels and profiles of Dechlorane Plus in a major E-waste dismantling area in China

Dechlorane Plus (DP) is a high-production volume, chlorinated flame retardant comprising two major isomers, syn- and anti-DP. In this study, levels of DP were measured in soil and earthworm samples in farmland from a typical E-waste dismantling area in China. The concentrations of total DP ranged from 0.17 to 1,990 ng g^?1 dw in soil samples and 3.43 to 89.2 ng g^?1 lw in earthworm samples. Higher DP levels were found in some main E-waste dismantling sites than those in other sites. The ratios of anti-DP to total DP (f _anti) ranged from 0.57 to 0.80 in soil samples and 0.47 to 0.81 in earthworm samples, respectively. The f _anti in most samples in this study was in the range of the reported technical DP values. These results showed that improper E-waste dismantling activities could result in the emission of DP. Most earthworm samples showed very low BSAFs (biota-to-soil accumulation factors) for total DP. The values of BSAF were in the range of 0.0007–1.85, with an average value of 0.23. This study presents the first report of the DP in earthworms, which would be useful for ecological risk assessment of DP in terrestrial ecosystem.     

Self-fertilisation in Celleporella hyalina

The accumulation of parasites in a fish host is modelled as a function of the total amount of prey consumed. The accumulated parasite load is then expressed as a function of fish length so that the asymptotic growth, L , of any population of commonly infected fish can be estimated. Estimates of L are obtained for orange roughy (Hoplostethus atlanticus), albacore tuna (Thunnus alalunga) and the New Zealand southern arrow squid (Nototodarus sloanii).     

Influence of phytoplankton on complexing capacity of seawater†

Differential Pulse Anodic Stripping Voltammetry (DPASV) was employed to measure Apparent Copper Complexing Capacity (L_t) and Stability Constants (K_s) of related cupric complexes of cell exudates of the phytoplanktonic alga Dunaliella salina. Three natural seawater samples collected 0.1, 2, 5 miles off the Tyrrhenian coast were used as culture medium. The measurements were carried out 1h and 7 days after the inoculum. Furthermore, on one culture the medium was passed through C₁₈‐SEP‐PAK cartridges in order to separate the cell exudates. The results show that Dunaliella salina influences the value of L_t but does not affect the value of K_s . The C₁₈SEP‐PAK retain only 50% of the ligands produced by the cells and capable of complexing copper.     

Adsorption of fluoride on clay minerals and their mechanisms using X-ray photoelectron spectroscopy

This research investigates the adsorption mechanisms of fluoride (F) on four clay minerals (kaolinite, montmorillonite, chlorite, and illite) under different F^? concentrations and reaction times by probing their fluoride superficial layer binding energies and element compositions using X-ray photoelectron spectroscopy (XPS). At high F^? concentrations (C ₀ = 5?C1000 mg·L^?1), the amount of F^? adsorbed (Q _F), amount of hydroxide released by clay minerals, solution F^? concentration, and the pH increase with increasing C ₀. The increases are remarkable at C ₀>50 mg·L^?1. The QF increases significantly by continuously modifying the pH level. At C ₀<5?C100 mg·L^?1, clay minerals adsorb H⁺ to protonate aluminum-bound surface-active hydroxyl sites in the superficial layers and induce F^? binding. As the C ₀ increases, F^?, along with other cations, is adsorbed to form a quasi-cryolite structure. At C ₀>100 mg·L^?1, new minerals precipitate and the product depends on the critical Al³⁺ concentration. At [Al³⁺]>10^?11.94 mol·L^?1, cryolite forms, while at [Al³⁺]<10^?11.94 mol·L^?1, AlF₃ is formed. At low C ₀ (0.3?C1.5 mg·L^?1), proton transfer occurs, and the F^? adsorption capabilities of the clay minerals increase with time.     

离子液体[C_8 mim]Cl对泥鳅胚胎和仔鱼的毒性

以泥鳅的胚胎及仔鱼为试验材料,选择胚胎发育的4个不同时期(囊胚期、原肠胚中期、神经胚期、尾芽期)及仔鱼期为处理开始的时间点,探讨了离子液体[C8mim]Cl的毒性作用。结果表明,随着[C8mim]Cl浓度增加,泥鳅胚胎的孵化率下降,畸形率上升,具有明显的剂量-效应关系,67~150 mg·L-1的[C8mim]Cl对泥鳅胚胎均表现出明显的致畸毒性效应;随着[C8mim]Cl浓度增加,泥鳅仔鱼死亡率上升,而100~225 mg·L-1的[C8mim]Cl对泥鳅仔鱼具有明显的致畸、致死作用。其中,[C8mim]Cl对孵出期泥鳅仔鱼的24 h、48 h的半致死浓度分别为97.95和86.77 mg·L-1;而[C8mim]Cl对孵出后3 d泥鳅仔鱼的24 h、48 h的半致死浓度分别为73.77和40.98 mg·L-1。由上可知,在一定的剂量内,[C8mim]Cl对泥鳅胚胎及仔鱼的发育有明显的致畸、致死作用,这为离子液体[C8mim]Cl的合理使用提供了理论依据。     

Role of heavy polar organic compounds for water repellency of sandy soils

Separation and chemical characterisation of specific compounds responsible for soil water repellency has not previously been achieved. Here we describe the extraction, separation and analysis by gas chromatography-mass spectrometry of organic compounds found in wettable and water repellent sandy soils from the Netherlands and United Kingdom. Fatty acids (C₁₆–C₂₄), amides (C₁₄–C₂₄), alkanes (C₂₅–C₃₃), aldehydes/ketones (C₂₃–C₃₁) and complex ring-containing structures were detected in all samples. We found a greater abundance of high molecular mass polar compounds in the water repellent samples.     

Kinetics of the oxidation of endocrine disruptor nonylphenol by ferrate(VI)

The kinetics of the oxidation of endocrine disruptor nonylphenol (NP) by potassium ferrate(VI) (K₂FeO₄) in water as a function of pH 8.0–10.9 at 25°C is presented. The observed second-order rate constants, k _obs, decrease with an increase in pH 269–32 M^?1 s^?1. The speciation of Fe(VI) (HFeO ₄ ^? and FeO ₄ ^2? ) and NP (NP–OH and NP–O^?) species was used to explain the pH dependence of the k _obs values. At a dose of 10 mg L^?1 (50 μM) K₂FeO₄, the half-life for the removal of NP by Fe(VI), under water treatment conditions, is less than 1 min.     

Organic composition in the dry season rainwater of Guangzhou, China

This paper reports the results from a study of the organic composition of rainwater collected at Tianhe district of Guangzhou city, P.R. China, during the dry season. Several special setups of a pyrex bottle with a glass funnel were used for the collection of the rainwater. Three fractions (aliphatics, PAHs and fatty acids) were separated from the total extracted organic compounds and identified with GC-MS. The molecular diagnostic ratios were utilized for the source reconciliation. The aliphatic hydrocarbon and the biomarkers (triterpanes and steranes) distribution show a characteristic of the petrochemical source in the rainwater samples. The PAHs diagnostic ratios [e.g. MP/P, MPI, Fl/ (Fl + Py)] indicated vehicular emissions. The fatty acids ratios (e.g. C_18:1/C_18:0 and C_18:2/C_18:0) reflect the contribution of cooking emissions, while the higher plant waxes play little part. Moreover, the values of MP/P, MPI, BaA/(BaA + CT) and BeP/(BeP + BaP) reflected the origin of the long-distance transportation to some extent. On the whole, for the dry season rainwater, all molecular diagnostic ratios indicated the complexity of the organic composition of the rain, which have the characteristics of both a local emission contribution and a long-distance transportation contribution.     

Uptake and toxicity of some pesticides on three freshwater fishes (Oreochromis niloticus,Clarias gariepinus and Chrysicthys nigrodigitatus)

Studies were carried out to determine the toxicity of some selected pesticides on fresh water fish in a tropical environment. The uptake of the pesticides lindane, pentachlorophenol (PCP), and propoxur, which are frequently used by farmers and industrialists were studied in concrete ponds at the University of Cape Coast, in Ghana. The fishes used for the study were Oreochromis niloticus, Clarias gariepinus, and Chrysicthys nigrodigitatus, and were obtained from cultured ponds in the Cape Coast District and Mankessim in the Central Region and Weija Dam, in the Greater Accra region of Ghana. Single high lethal concentration (SD) or acute treatment and cumulative/chronic (or multiple minor) lethal concentration (CD) treatment were employed in administering the pesticides to the fishes via water. Gas chromatograph (GC) Electron Capture Detector (ECD) analysis was done on the dead fishes to see the extent of ingestion. The LC₅₀ values obtained for lindane on the three fish samples were as follows: Chrysicthys?–?0.38?mg?L^?1; Oreochromis?–?0.42?mg?L^?1, and Clarias?–?1.2?mg?L^?1. Mortalities occurred in fish within 3–5 days of application. For the PCP on Chrysicthys, Oreochromis, and Clarias species the LC₅₀ values were 0.42, 0.32 and 0.64?mg?L^?1, respectively for over a 2–3 day period. For a three-time influx period of propoxur the LC₅₀ for Chrysicthys, Oreochromis, and Clarias, were 22.0, 30.40, and 45.04 (all in mg?L^?1), respectively. The results obtained indicated that the pesticides had adverse effects on the general growth and reproduction of fishes. Gonadosomatic indices also showed that the pesticides affected the development of the body, the gonads, and their reproduction.     

南方某铀矿山废水对生物的急性毒性研究

为探明铀矿山对周围环境的联合毒性机制,本研究以常用生物毒性测试菌种——发光细菌青海弧菌Q67和费氏弧菌以及禾花鲤为受试生物代表,实地采集的铀矿山废水为目标废水,研究铀矿山废水对发光细菌和禾花鲤的急性毒性。实验结果表明,矿山废水对3种生物的急性毒性存在显著的剂量-效应关系,毒性效应浓度EC_(50)(LC50)的大小顺序为禾花鲤幼鱼费氏弧菌青海弧菌Q67,Pb~(2+)/U~(6+)浓度分别为6.052/3.026 mg·L~(-1)、2.284/1.142 mg·L~(-1)、1.339/0.669 mg·L~(-1),均可有效指示矿山废水的毒性水平,其中发光细菌更为灵敏、快速;且青海弧菌Q67的EC_(50)值最小,灵敏度最高,可作为表征矿山废水毒性风险的首选指示物。研究结果能够为放射性矿区废水生态风险预警、安全处理处置、水质基准制定及流域水环境管理提供依据。     

Biokonzentration von persistenten superlipophilen Chemikalien in aquatischen Organismen

According to generally accepted theory, persistent superlipophilic chemicals with logn-octanol/water partitioning coefficient (log K_ow) >6 and molecular sizes >9,5 Å, such as octachlorodibenzo-p-dioxin, decachlorobiphenyl, Mirex etc., do not significantly bioconcentrate in aquatic organisms from ambient water. In the light of new results and considerations, this hypothesis has to be revised. The most convincing argument against this hypothesis is that in all bioconcentration experiments with superlipophilic chemicals compound concentrations have been applied which exceeded water solubility by several orders of magnitude. In this paper we describe various methods how to determine bioconcentration (BCF) factors of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin and Mirex, BCF values evaluated by this means match well those calculated by QSARs for fish and mussels based on log K_ow and water solubility as well. As expected these BCF values exceed previous ones by several orders of magnitude. As practical consequences, we recommend for BCF evaluations of superlipophilic chemicals:

1. flow-through systems, kinetic method (OECD guideline No 305 E)
2. ambient concentrations≤water solubility.

*** DIRECT SUPPORT *** A00HP013 00002     

外源化合物在鱼体内生物半减期的QSAR模型

生物半减期(t1/2)是评价外源化合物在鱼体内蓄积效应的重要参数。实验测定t_(1/2)的速度慢、成本高,难以满足化学品生态风险评价的需求,需要发展替代实验的模型预测方法。本研究搜集了653种化合物t1/2实测值,采用多元线性回归(MLR)和支持向量机(SVM) 2种方法,建立了鱼体logt1/2的定量构效关系(QSAR)预测模型。MLR模型的校正决定系数(R(adj)~2)为0.751,均方根误差(RMSE_(train))为0.587,去一法交叉验证系数(Q_(LOO)~2)为0.735,外部验证系数(Q_(ext)~2)为0.682,这表明模型具有较好的拟合度、稳健性和预测能力。SVM模型具有更好的拟合和预测能力(R_(adj)~2=0.839,RMSE_(train)=0.457,Q_(ext)~2=0.708)。采用Williams法对模型的应用域进行表征。所建模型可用于预测多环芳烃、多氯联苯、多溴联苯醚、有机磷农药、药物等典型化合物,以及其他烷烃、环烷烃、烯烃、醇、醚、酸、酯、酮、含卤素化合物、芳香族化合物、含硫、氮、磷化合物的在鱼体内的logt1/2值。     

Pollution assessment of the lower basin of Lakes Kainji/Jebba, Nigeria: heavy metal status of the waters, sediments and fishes

The objective of this investigation was to examine the heavy metal status of the lower basin of Kainji dam (used for hydroelectricity generation), which includes Lakes Kainji/Jebba, Nigeria, and the potential for human exposure to heavy metals from eating fish caught in the lakes. Water, sediments and fish were sampled from the lakes and evaluated for As, Cu, Co, Cr, Fe, Hg, Mn, Ni, Pb, Sb, Ti, V and Zn using the EDXRF technique. Fe and Mn were found to be present at high mean concentrations in the water (13 and 9 μg L^-1), sediment (7092 and 376 μg g^-1) and fish (11.4 and 4.6 μg g^-1) samples. Sb (3.2 μg L^-1), Ti (4.1 μg L^-1), Cr (2.2 μg L^-1), Co (1.2 μg L^-1), Cu (1.3 μg L^-1) and Pb (1.2 μg L^-1) in the water samples and Sb (29 μg g^-1), Ti (27 μg g^-1), V (27 μg g^-1), Cr (27 μg g^-1), Co (40 μg g^-1), Ni (33 μg g^-1), Cu (25 μg g^-1), Zn (59 μg g^-1) and Pb (19 μg g^-1) in the sediment samples were found to be of medium mean concentrations. The other metals were present at trace levels (<1 μg), including As and Hg in the fish and sediment samples. There was an appreciable increase in␣metal concentrations in going from the water to the sediment samples. The probable source of the pollutants is anthropogenic, arising from agricultural activities, corrosion/abrasion of the ferrous steel material and additives in the lubricants and insulation used for auxiliary services on the turbine floor of the dam constructed on the lakes. However, natural geological sourcing from the underlying lake rock cannot be totally ignored, particularly the high levels of Fe and Mn in the sediment samples. The potential risk for human exposure to these metals emanates from the fish caught in the lakes and subsequently consumed, as there are already significant levels of these metals in the two fish species analysed, Tilapia (Oreochromis niloticus) and Chrysicthys (Chrysicthys auratus).     

Particulate and semivolatile associated aliphatic hydrocarbon exhaust emission from heavy duty diesel vehicles

The exhaust emissions from two heavy duty diesel vehicles running on eight different fuel compositions were investigated regarding their content of high molecular weight (≥ C₁₂) aliphatic/ olefinic hydrocarbons. It was concluded that the emitted amount of semi‐volatile associated aliphatic hydrocarbons (range C₁₂‐C₂₂) depend on the fuel used in the engines and that these emissions mainly consisted of uncombusted fuel components. It was also found that uncombusted engine lubrication oil was the main constituent of the emitted particulate associated aliphatic hydrocarbons (C₁₇‐C₄₀). These constituted between 58% and 95% of the total emissions of the high molecular weight aliphatic compounds. Emission factors for the total of high molecular aliphatic hydrocarbons (C₁₂‐C₄₀) were demonstrated to be in the range of 15–100 mg/km. Some individual aliphatic hydrocarbons with cocarcinogenic effects were identified and quantified in both particulate and semi‐volatile phases of the exhaust. Multivariate data analysis was used to investigate the relationship between fuel parameters and emission of semi‐volatile aliphatic emission.