Formation of chlorinated estrones via hypochlorous disinfection of wastewater effluent containing estrone

Chlorinated derivatives of estrone (E1) in the effluent of a municipal sewage treatment plant located in Shizuoka prefecture, Japan were detected by gas chromatography/mass spectrometry using electron impact in selected ion monitoring (GC/MS-EI-SIM) analysis. The concentrations of E1, 2-chloroestrone, 4-chloroestrone and 2,4-dichloroestrone in the effluent sample collected in December 2005 were 60.0 ng l(-1), 4.0 ng l(-1), 14.5 ng l(-1), and 9.8 ng l(-1), respectively. In the effluent sample taken in June 2005, 2,4-dichloroestrone was detected at 5.6 ng l(-1) along with 17.6 ng l(-1) of E1. However, only E1 was detected at 5.9 ng l(-1) in the sample in May 2005. To elucidate the behavior of E1 during the disinfection process with sodium hypochlorite in the sewage treatment plant, we carried out a reaction of E1 with sodium hypochlorite in buffer solutions at pH 7 and 9. As E1 was consumed rapidly, chlorinated estrones were produced and relatively fast formation of 2-chloroestrone, 4-chloroestrone, and 2,4-dichloroestrone was observed. Furthermore, 1,4-estradiene-3,17-dione derivatives were formed from the reaction between 2,4-dichloroestrone and sodium hypochlorite.     

Impact of redox conditions on metolachlor and metribuzin degradation in Mississippi flood plain soils

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd(-1) and 25 ngd(-1), respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd(-1) and 32.5 ngd(-1), respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd(-1) and 12.0 ngd(-1) for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd(-1) and 5.35 ngd(-1). Metribuzin degraded faster (12.0 ngd(-1)) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd(-1)).     

Structure and origin of the natural halogenated monoterpene MHC-1 and its concentrations in marine mammals and fish

The halogenated natural product previously named mixed-halogenated compound 1 (MHC-1) was isolated from the red seaweed Plocamium cartilagineum harvested in Helgoland, Germany. A total of 1.9mg of pure MHC-1 was obtained from 1g air-dried seaweed. The (1)H and (13)C NMR data matched those reported for a natural monoterpene isolated from this species. Thus, the structure of MHC-1 was established to be (1R,2S,4R,5R,1'E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(2'-chloroethenyl)-5-methylcyclohexane. Moreover, the isolated monoterpene proved to be identical with the compound previously detected in marine mammals and fish from different locations. In addition we examined two samples of P. cartilagineum from Ireland and from the Antarctic; however MHC-1 was only present at low levels. Not only the concentrations were lower but also the pattern of polybrominated compounds differed from MHC-1. A calibrated solution of MHC-1 was used to determine correct concentrations from samples where previously only estimates existed relative to the gas chromatography-electron capture detector (GC/ECD) response of trans-chlordane, which underrated the MHC-1 concentrations by more than factor 2. The highest MHC-1 concentration determined to date in marine mammals is 0.14mgkg(-1) blubber. Significantly higher MHC-1 concentrations were determined in farmed fish with up to 2.2mgkg(-1) lipids. The samples with high concentrations of MHC-1 have in common that they were collected in proximity of the natural habitats of P. cartilagineum.     

Nitrate in waters from sewage-sludge amended lysimeters

Nitrate nitrogen was measured in runoff and tile-drainage during two years of operation of instrumented, large-scale lysimeters planted to corn (Zea mays L.) and amended with sewage sludge which was applied at rates supplying total N amounting to 2292 kg ha(-) in 1972 and 3286 kg ha(-1) in 1973. Other lysimeters were amended with inorganic fertiliser at the rate of 336 kg N ha(-1) year(-1). Annual losses in runoff and tile-drainage from sludge treatments were 0.9 and 5.1 and 371 and 663 kg NO(3)(-)-N ha(-1). Losses from lysimeters treated with inorganic fertiliser were 1.1 and 3.3 kg NO(3)(-)-N ha(-1) year(-1) in runoff and 31 and 79 kg NO(3)(-)-N ha(-1) year(-1) in tile-drainage. Given the nitrogen inputs accounted for in the study design, unaccounted for losses of 1800 to 2400 kg ha(-1) year(-1) were calculated for sludge and 277 kg ha(-1) year(-1) for inorganic fertiliser treatments. For one year there was a 300 kg ha(-1) increase in N in the lysimeters receiving inorganic fertiliser. Median NO(3)(-)-N concentrations ranged from 8.9 to 14.0 mg litre(-1) in runoff from sludge-treated lysimeters and 3.6 to 5.9 mg litre(-1) in runoff from lysimeters receiving inorganic fertiliser. In tile-drainage the median NO(3)(-)-N concentrations were 148 to 223 mg litre(-1) and 24 to 44 mg litre(-1) for sludge and inorganic fertiliser treatments, respectively. Highest runoff levels occurred in early summer storms, whereas highest tile-drainage concentrations occurred in late winter and early spring.     

New cytochrome P450 1B1, 1C1, 2Aa, 2Y3, and 2K genes from Chinese rare minnow (Gobiocypris rarus): Molecular characterization,basal expression and response of rare minnow CYP1s and CYP2s mRNA exposed to the AHR agonist benzo[a]pyrene

Cytochrome P450 (CYP450) genes play an important role in catalyzing oxidative metabolism of toxicants. Recently, CYP1 subfamily were discovered and reported in fish, however, little is known regarding the CYP2 isoforms in fish. In the present study, the cDNA fragments of CYP 1B1 and 1C1 and CYP2Aa, 2Y3, and 2K of rare minnow were cloned and exhibited a high amino acid sequence identity compared with their zebrafish orthologs. Basal expression showed CYP1C1 and CYP 2Aa expression were observed in all eight tissues analyzed (liver, gill, intestine, kidney, spleen, brain, skin, and muscle). CYP 1A, and 1B1 expression was found in all tissues except for muscle and skin. However, CYP 2Y3 was expressed in liver, spleen, intestine and muscle whereas CYP 2 K in liver, kidney and intestine. 4 and 100 μg L⁻¹ Benzo[a]pyrene (BaP) induced patterns showed that CYP 1A, 1B1 and 1C1 expression in liver, gill, and intestine was strongly up-regulated (p < 0.05). Furthermore, CYP 2Y3 was strongly induced in liver from BaP treatments (p < 0.05). The high induction on mRNA level of CYP1s and CYP 2Y3 by BaP could be associated with catalyzing detoxification and indicated that CYP2s may also be potential biomarker to screen AHR agonist. The high responsiveness of CYP1 and 2 genes suggested Chinese rare minnow is feasible to screen and assess pollution with AHR agonist.     

Metal exposure and breast cancer among Northern Mexican women: assessment of genetic susceptibility

Environmental Science and Pollution Research - This study aims to assess breast cancer (BC) association with metals and whether polymorphisms in CYP1A1, CYP1B1, GSTM1 and GSTT1 act as confounders...     

Copper regulation and homeostasis of Daphnia magna and Pseudokirchneriella subcapitata: influence of acclimation

This study aimed to evaluate (1) the capacity of the green alga Pseudokirchneriella subcapitata and the waterflea Daphnia magna to regulate copper when exposed to environmentally realistic copper concentrations and (2) the influence of multi-generation acclimation to these copper concentrations on copper bioaccumulation and homeostasis. Based on bioconcentration factors, active copper regulation was observed in algae up to 5 microg Cu L(-1) and in daphnids up to 35 mug Cu L(-1). Constant body copper concentrations (13+/-4 microg Cu g DW(-1)) were observed in algae exposed to 1 through 5 microg Cu L(-1) and in daphnids exposed to 1 through 12 microg Cu L(-1). At higher exposure concentrations, there was an increase in internal body copper concentration, while no increase was observed in bioconcentration factors, suggesting the presence of a storage mechanism. At copper concentrations of 100 microg Cu L(-1) (P. subcapitata) and 150 microg Cu L(-1) (D. magna), the significant increases observed in body copper concentrations and in bioconcentration factors may be related to a failure of this regulation mechanism. For both organisms, internal body copper concentrations lower than 13 microg Cu g DW(-1) may result in copper deficiency. For P. subcapitata acclimated to 0.5 and 100 microg Cu L(-1), body copper concentrations ranged (mean+/-standard deviation) between 5+/-2 microg Cu g DW(-1) and 1300+/-197 microg Cu g DW(-1), respectively. For D. magna, this value ranged between 9+/-2 microg Cu g DW(-1) and 175+/-17 microg Cu g DW(-1) for daphnids acclimated to 0.5 and 150 microg Cu L(-1). Multi-generation acclimation to copper concentrations >or =12 microg Cu L(-1) resulted in a decrease (up to 40%) in body copper concentrations for both organisms compared to the body copper concentration of the first generation. It can be concluded that there is an indication that P. subcapitata and D. magna can regulate their whole body copper concentration to maintain copper homeostasis within their optimal copper range and acclimation enhances these mechanisms.     

Aflatoxin M1 contamination of milk and ice cream in Abeokuta and Odeda local governments of Ogun State, Nigeria

A survey was undertaken to determine the aflatoxin M(1) contamination of milk and some locally produced dairy products in Abeokuta and Odeda local governments of Ogun State, Nigeria. Samples of human and cow milk, yoghurt, "wara", ice cream and "nono" were collected randomly within the local governments and analysed for aflatoxin M(1) using the two-dimensional TLC. Aflatoxin M(1) contamination in the range of 2.04-4.00 microg l(-1) was noticed only in milk and ice cream. In particular, samples of human milk, cow milk and ice cream recorded high scores of 4.0 microg l(-1), 2.04 microg l(-1) and 2.23 microg l(-1), respectively in Abeokuta local governments and a score of 4.0 microg l(-1) for cow milk in Odeda local government. This indicates a high level contamination in the local governments since the weighted mean concentration of aflatoxin M1 in milk for African diet is 0.002 microg l(-1). Therefore the concentration of AFB1 in feeds which is transformed to AFM1 in milk should be reduced by good manufacturing and good storage practices. Furthermore, there is need for stringent quality control during processing and distribution of these products.     

Seasonal variation in dissolved gaseous mercury and total mercury concentrations in Juam Reservoir, Korea

Dissolved gaseous mercury (DGM) and total mercury (TM) concentrations were measured in Juam Reservoir, Korea. DGM concentrations were higher in spring (64+/-13pgL(-1)) and summer (109+/-15pgL(-1)), and lower in fall (20+/-2pgL(-1)) and winter (23+/-6pgL(-1)). In contrast, TM concentrations were higher in fall (3.2+/-0.1ngL(-1)) and winter (3.3+/-0.1ngL(-1)) than in spring (2.3+/-0.1ngL(-1)) and summer (2.2+/-0.4ngL(-1)). DGM concentrations were correlated with water temperature (p<0.0001), ORP (p<0.0001), UV intensity (UV-A: p=0.008; UV-B: p=0.003), and DOC concentration (p=0.0107). DGM concentrations varied diurnally with UV intensity. The average summer DGM (109+/-15pgL(-1)) and TM (2.2+/-0.4ngL(-1)) concentrations in Juam Reservoir were higher than the averages for North American lakes (DGM=38+/-16pgL(-1); TM=1.0+/-1.2ngL(-1)), but lower than levels reported for Baihua Reservoir in China.     

Metal bioaccumulation and metallothionein concentrations in larvae of Crassostrea gigas

Larval stages of bivalve molluscs are highly sensitive to pollutants. Oysters from a hatchery from Normandy (English Channel) were induced to spawn, and fertilized eggs were exposed to copper or cadmium for 24 h. Metal accumulation (from 0.125 to 5 microg Cu L(-1) and from 25 to 200 microg Cd L(-1)) and MT concentrations were measured in larvae. Compared to controls, larvae accumulated copper and cadmium with an increase in MT concentrations particularly with cadmium (i.e. 130.96 ng Cu (mg protein)(-1) and 12.69 microg MT (mg protein)(-1) at 1 microg Cu L(-1) versus 23.19 ng Cu (mg protein)(-1) and 8.92 microg MT (mg protein)(-1) in control larvae; 334.3 ng Cd (mg protein)(-1) and 11.70 microg MT (mg protein)(-1) at 200 microg Cd L(-1) versus 0.87 ng Cd (mg protein)(-1) and 4.60 microg MT (mg protein)(-1) in control larvae). Larvae were also obtained from oysters of a clean area (Arcachon Bay) and a polluted zone (Bidassoa estuary) and exposed to copper in the laboratory, their MT concentration was measured as well as biomarkers of oxidative stress. Biomarker responses and sensitivity to copper for the larvae from Arcachon oysters were higher than for those from Bidassoa.     

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.     

Changes in oxygen consumption and respiratory enzymes as stress indicators in an estuarine edible crab Scylla serrata exposed to naphthalene

The sublethal effect of naphthalene was studied on the physiology of a mud crab Scylla serrata. The 96 h acute toxicity of naphthalene was determined and found to be 28 mg 1(-1) (LC100), 18 mg 1(-1) (LC50), 10 mg 1(-1) (LC0) respectively. The 30 days sublethal effect (LC0) 9 mg 1(-1), 8 mg 1(-1), 10 mg 1(-1), of naphthalene was investigated in the crab S. serrata with reference to oxygen consumption and changes in the activity of respiratory enzymes. The results indicated that naphthalene caused disturbance in the normal physiology of the crab. The bioaccumulation of naphthalene was also investigated in gills, hepatopancreas, haemolymph and ovary. The consumption of oxygen increased in the naphthalene medium when compared with that of the crabs exposed to naphthalene free medium. A decreased trend in the activity of respiratory enzymes such as lactate dehydrogenase (LDH), isocitrate dehydrogenase (ICDH), succinate dehydrogenase (SDH), malate dehydrogenase (MDH), alpha-ketoglutarate dehydrogenase (alpha-KDH) and glutathione (GSH) were recorded in the hepatopancreas, ovary and gills of S. serrata for all the tested concentrations of naphthalene and the results were analyzed for their significance.     

Simultaneous analysis of free and sulfo-conjugated steroid estrogens in artificial urine solution and agricultural soils by high-performance liquid chromatography

A simple and robust analytical method was developed to simultaneously detect and quantify 17β-estradiol (E2), estrone (E1), 17β-estradiol-3-sulphate (E2-3S), and estrone-3-sulphate (E1-3S) in aqueous solutions (calcium chloride and artificial urine solutions) and agricultural soils using high performance liquid chromatography and UV detection. The standards for all four compounds were linear in the range of 0.01 to 1.0 μg mL(-1) (n = 6) and 1.0 to 20 μg mL(-1) (n = 6), respectively, with correlation coefficients > 0.999. The on-column limits of detection at an injection volume of 50 μL and S/N (signal: noise) ratio of 3 were: 9.0 ng mL(-1), 10 ng mL(-1), 5.0 ng mL(-1), and 7.0 ng mL(-1) for E2-3S, E1-3S, E2 and E1, respectively. The limit of detection and quantification in artificial urine solution and CaCl(2) solution was 1.0 ng mL(-1) for all four compounds. Method detection limits for the compounds in the 3 soils ranged from 2 to 2.4 ng g(-1) (E2-3S and E1-3S), and 1.0 to 2.9 ng g(-1) (E2 and E1), respectively.     

Monitoring of organochlorine pesticides using PFU systems in Yunnan lakes and rivers, China

Polyurethane foam unit (PFU) systems were collected from 11 lakes and three rivers in the Yunnan Plateau, China and, the PFU extrusion liquids were analyzed for organochlorine pesticides (OCPs) by gas chromatography with electron capture detection (GC-ECD). The concentrations of pp'-DDE, HCB and HCHs were undetectable to 1.86 microgl-1 (mean 0.27 microgl-1), undetectable to 0.72 microgl-1 (mean 0.11 microgl-1), and 0.24-21.95 microgl-1 (mean 7.39 microgl-1) respectively in lakes; and those in rivers were undetectable to 0.23 microgl-1 (mean 0.08 microgl-1), 0.68-2.93 microgl-1 (mean 1.70 microgl-1), and 2.71-37.56 microgl-1 (mean 17.01 microgl-1) respectively. Notably, some residue levels of OCPs exceeded the US National Recommended Water Quality Criteria, implying Yunnan has levels of OCPs potentially harmful to human health. Further, the contamination by OCPs showed an obvious spatial distribution pattern. Amongst the lakes, Dianchi, Xingyun, Lugu and Yangzonghai had the highest OCP levels dominated by beta-HCH, whereas among rivers, Nujiang and Lancang Rivers had the highest contents of OCPs dominated by alpha-HCH. This demonstrates that HCHs are the predominant contaminants and some point sources of HCHs may still exist in Yunnan. The pollution levels in Yunnan were compared with other studies, suggesting the PFU method is suitable for long-term on-line monitoring of trace OCPs in aquatic ecosystems. Therefore, continuous studies monitoring OCPs in lakes and rivers are needed to further understand the future trend of contamination.     

Bioaccumulation of the lipophilic metabolites of nonionic surfactants in freshwater organisms

Nonylphenol (NP), nonlyphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) were determined in different freshwater organisms from the surface waters in the Glatt Valley, Switzerland. Rather high concentrations of the compounds investigated have been found to occur in macrophytic algae, particularly Cladophora glomerata (up to 38 mg kg(-1), 80 mg kg(-1), and 28 mg kg(-1) of NP, NP1EO and NP2EO, respectively), the bioconcentration factors of NP reaching up to 10,000. The concentrations in fish were much lower (NP: < 0.03-1.6 mg kg(-1), NP1EO: 0.06-7.0 mg kg(-1), and NP2EO: <0.03-3.1 mg kg(-1) indicating that biomagnification did not take place. Similar concentrations to those in the fish were determined in different tissues of a wild duck. The estimated bioconcentration factors in fish tissues ranged from 13 to 410 for NP, 3 to 300 for NP1EO and 3 to 330 for NP2EO.     

Emission profiles of polychlorinated dibenzodioxins, polychlorinated dibenzofurans (PCDD/Fs), dioxin-like PCBs and hexachlorobenzene (HCB) from secondary metallurgy industries in Portugal

This paper reports, for the first time, a study of dioxin emissions from 10 siderurgies and metallurgies, secondary copper, aluminum and lead metallurgies, in Portugal. The study reports the emission factors and total emission amounts of PCDD/Fs, dioxin-like PCBs and hexachlorobenzene (HCB). The congener patterns were characterized and are discussed. The results showed that the total amount of PCDFs is higher than PCDDs in flue gas of each industrial unit. The toxic equivalent emission factors of pollutants emitted are 3098-3338 ngI-TEQt(-1) for PCDD/Fs and 597-659 ng I-TEQt(-1) for dioxin-like PCBs in siderurgies production (total estimated emission amounts released to atmosphere of 3.9-4.5 g I-TEQyr(-1)), 50-152 ng I-TEQt(-1) for PCDD/Fs and 24-121 ng I-TEQt(-1) for dioxin-like PCBs in ferrous foundries production (total estimated emission amounts released to atmosphere of 0.0010-0.0016 g I-TEQyr(-1)) and 5.8-5715 ng I-TEQt(-1) for PCDD/Fs and 0.49-259 ng I-TEQt(-1) for dioxin-like PCBs in non-ferrous foundries production (total estimated emission amounts released to atmosphere of 0.00014-0.12 g I-TEQyr(-1)). The HCB emission from siderurgies production is 0.94-3.2 mg t(-1) (total estimated emission amounts released 0.94-3.8 g yr(-1)), being much smaller, residual, in the emissions of the other types of plants (0.0012-0.026 mg t(-1) production and total estimated emission amounts released to atmosphere of 0.013-1.7 mg yr(-1)).     

Toxicity of HC Orange No. 1 to Daphnia magna, zebrafish (Brachydanio rerio) embryos, and goldfish (Carassius auratus)

HC Orange No. 1 (HCO1; 2-nitro-4′-hydroxydiphenylamine) (CAS No. 54381-08-7) is used as a color additive in hair dyes and can be released into aquatic environments in wastewater. In this paper, the effects of HCO1 on aquatic organisms were studied using a battery of toxicological tests. These included measuring immobilization of Daphnia magna, inhibition of zebrafish embryo development, and acute lethality in zebrafish and goldfish, which are different species belonging to different trophic levels. HCO1 was toxic to all of the organisms studied. In our experiments, HCO1 remarkably restrained the mobility of D. magna, which may cause subsequent death. The EC₅₀ value for restrained the mobility of D. magna at 48 h was 1.54 mg HCO1 l⁻¹. In addition, HCO1 showed toxicity in zebrafish and goldfish, where LC₅₀values at 96 h were 4.04 and 5.37 mg l⁻¹, respectively. The results also indicated that HCO1 remarkably retarded the development of zebrafish embryos, which may cause embryo abnormality and even lethality. The most sensitive toxicological endpoint in the development of the embryos was failure to hatch, which had an EC₅₀ of 0.19 mg HCO1 l⁻¹. These results indicated that HCO1 is a potential teratogen to zebrafish embryos. In addition, as HCO1 concentrations increased, the outcomes of each of these toxicity tests changed in a concentration-dependent manner. Together, the results revealed that HCO1 appears to be toxic to multiple different species of aquatic organisms. The EC₅₀ (LC₅₀) values contain sufficient discriminatory power for risk assessment of HCO1 in aquatic environments. Based on the present results, more efficient risk assessment procedures for HCO1 will be designed in the future, integrating more flexible testing methods into the testing schemes that employ only the necessary tools for each case.