Occurrence of free estrogens,conjugated estrogens,and bisphenol A in fresh livestock excreta and their removal by composting in North China

An efficient pretreatment and analytical method was developed to investigate the occurrence and fate of four free estrogens (estrone (E1), 17β-estradiol (17β-E2), estriol (E3), and 17α-ethinylestradiol (EE2)), four conjugated estrogens (estrone-3-sulfate sodium salt (E1-3S), 17β-estradiol-3-sulfate sodium salt (E2-3S), estrone-3-glucuronide sodium salt (E1-3G), and 17β-estradiol-3-glucuronide sodium salt (E2-3G)), and bisphenol A (BPA) in three livestock farms raising beef cattle, cows, sheep, swine, and chickens in Qi County, which is located in North China. The results demonstrated that one cow and one beef cattle excreted 956.25–1,270.41 and 244.38–319.99 μg/day of total (free and conjugated) estrogen, respectively, primarily through feces (greater than 91 %), while swine excreted 260.09–289.99 μg/day of estrogens, primarily through urine (98–99 %). The total estrogen excreted in sheep and broiler chicken feces was calculated to be 21.64–28.67 and 4.62–5.40 μg/day, respectively. It was determined that conjugated estrogens contributed to 21.1–21.9 % of the total estrogen excreted in cow feces and more than 98 % of the total estrogen excreted in swine urine. After composting, the concentration of total estrogen decreased by 18.7–59.6 %; however, increased levels of BPA were measured. In treated compost samples, estrogens were detected at concentrations up to 74.0 ng/g, which indicates a potential risk of estrogens entering the surrounding environment.     

Factors controlling the biodegradation of 17beta-estradiol, estrone and 17alpha-ethinylestradiol in different natural soils

We conducted a series of laboratory microcosm incubations with [(14)C]-labeled 17beta-estradiol (E2), estrone (E1) and 17alpha-ethinylestradiol (EE2) in 17 different natural soils to characterize hormone mineralization. A significantly higher mineralization was observed for E1 (2.0-37.6%) and E2 (4.2-50.2%) than for EE2 (0.5-2.6%) in all test soils after 21 days. Soil physical or chemical parameters were not related to estrogen mineralization. Although sorption parameters varied greatly for E2 (K(F)=21.9-317.5 mL g(-1)), for E1 (K(F)=46.0-517.5 mL g(-1)) and for EE2 (K(F)=29.9-326.1 mL g(-1)) this apparently did not control estrogen bioavailability since it showed no effects on hormone mineralization. In order to elucidate the controlling factors, experiments with combined additions of radiolabeled estrogens and different substrates were conducted. Additions of ammonium nitrate or alanine to soil samples generally increased EE2 mineralization, thus indicating N-limitation. Additions of glucose induced higher E2 and EE2 degradation in comparison to control samples which is attributed to co-metabolism. Additions of saw dust, catechol or streptomycin influenced the microbial population in the test soils and affected the mineralization of E2 and EE2. Thus, we clearly demonstrate that different microbial communities are responsible for E2 and EE2 degradation in soils. We suggest that EE2 is mineralized by white-rot fungi and E2 by bacteria.     

Hydrological and environmental conditions as key drivers for spatial and seasonal changes in PCDD/PCDF concentrations, transport and deposition along urban cascade reservoirs

To investigate the drivers for transport and deposition of 17 2,3,7,8-substituted PCDDs/PCDFs along an urban river, water samples from five reservoirs located along the river course were collected in January and July 2008. The concentrations of 17 congeners of PCDD/PCDF were determined and compared to environmental - physical, chemical and biological - conditions. The obtained data revealed that the concentration of the sum of toxic PCDDs/PCDFs in water samples differ between reservoirs as well as between seasons, ranging from 12.04 pg L(-1) in UP (first in the cascade) to 1327.94 pg L(-1) in PR (last in the cascade) during winter of 2008; and from 34.94 pg L(-1) in UP to 1352.50 pg L(-1) in TR (next to last) in summer 2008. In comparison, water samples collected from the river had a concentration several times lower at the first two sites (sites no. 1 and 4) and no detectable values at the last three stations (sites no. 7, 8, 10). The obtained data demonstrated strong or moderate correlations between the sum of 17 PCDDs/PCDFs and TEQ in reservoir water samples and physical, chemical and biological conditions, such as: Mg(2+) (R=0.82; R=0.80, respectively), SO(4)(2-) (R=0.80; R=0.80, respectively), K(+) (R=0.80; R=0.80, respectively), Ca(2+) (R=0.67, R=0.70, respectively), OSM (R=0.63, R=0.70, respectively). In addition, the positive strong correlation between TEQ concentrations and the water temperature (R=0.63) and chlorophyll a content (R=0.90) was noted. The violent weather conditions occurred during the research season with periods of intensive storm events (up to 32 mm in mid July), and thus the increased river flow velocity (up to 0.45 m(3)s(-1)) could have a direct and indirect influence on PCDDs/PCDFs concentration through changes in the sedimentation/resuspension ratio and consequently in transport, deposition and degradation processes along the river/reservoirs.     

Sodium and chloride accumulation in leaf, woody, and root tissue of Populus after irrigation with landfill leachate

The response of Populus to irrigation sources containing elevated levels of sodium (Na(+)) and chloride (Cl(-)) is poorly understood. We irrigated eight Populus clones with fertilized well water (control) (N, P, K) or municipal solid waste landfill leachate weekly during 2005 and 2006 in Rhinelander, Wisconsin, USA (45.6 degrees N, 89.4 degrees W). During August 2006, we tested for differences in total Na(+) and Cl(-) concentration in preplanting and harvest soils, and in leaf, woody (stems+branches), and root tissue. The leachate-irrigated soils at harvest had the greatest Na(+) and Cl(-) levels. Genotypes exhibited elevated total tree Cl(-) concentration and increased biomass (clones NC14104, NM2, NM6), elevated Cl(-) and decreased biomass (NC14018, NC14106, DM115), or mid levels of Cl(-) and biomass (NC13460, DN5). Leachate tissue concentrations were 17 (Na(+)) and four (Cl(-)) times greater than water. Sodium and Cl(-) levels were greatest in roots and leaves, respectively.     

Determination of source contributions to ambient PM2.5 in Kaohsiung, Taiwan, using a receptor model

Ambient particulates of PM2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM2.5. The mean concentration of ambient PM2.5 was 42.69-53.68 micrograms/m3 for the sampling period. The abundant species in ambient PM2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO4(2-) (12.8-15.1%), NO3- (8.1-10.3%), NH4+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO4(2-) and NO3-), and outdoor burning of agriculture wastes (13-17%).     

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.     

Ionic composition of PM(10) in the area of Thessaloniki,Greece

Airborne particulate matter (PM(10)) was collected from July 1997 to July 1998 at three locations in the city of Thessaloniki. PM(10) samples were analyzed for Cl(-), NO3(-), SO4(2-), Ca(2+), Mg(2+), Na(+), K(+) and NH4(+). The average PM(10) concentrations were found similar in all three sites with higher values in cold period. The ionic content comprised the 17-23% of the PM(10) mass and sulfate made up the 35-38% of the PM(10) ionic content with an average concentration of 4.80-7.26 microg m(-3). Good correlation was found for SO4(2-) and NO3(-) with Ca(2+), Mg(2+) and Cl(-). Two factors were found to influence the variance of ionic constituents in PM(10) by using factor analysis. Data evaluation considering wind direction showed that higher PM(10) and other ionic concentrations are associated with calm conditions, suggesting influences of local sources.     

Dietary exposure to PCBs based on food consumption survey and food basket analysis at Taizhou, China--the world's major site for recycling transformers

The levels of PCBs in different types of food (fish, shellfish, meat, rice, vegetables, and fruits) were analyzed to determine the dietary intake of 37 PCBs for local residents and e-waste workers (all lactating mothers) at Taizhou (China), a major electronic waste scrapping center, in particular for recycling transformers. The exposure to PCBs through dietary intake in Taizhou was estimated at 92.79 ngkg(-1)d(-1), contributed by consumption of freshwater fish (28%), rice (28%), meat (17%), shellfish (9%), vegetables (8%), egg (4%) and marine fish (2%). With regards to WHO-PCB-TEQ values, freshwater fish (40%), shellfish (24%), duck liver (18%) and rice (12%) were the main dietary sources with total daily intake (9.78 pg WHO-PCB-TEQ kg(-1)d(-1)), exceeding the FAO/WHO Tolerable Daily Intake (70 pg TEQkg(-1)body(-1)wt(-1)month(-1)).     

Removal effects and potential mechanisms of bisphenol A and 17α-ethynylestradiol by Biogenic Mn oxides generated by Bacillus sp. WH4

Environmental Science and Pollution Research - Endocrine disrupting compounds (EDCs), such as bisphenol A (BPA) and 17α-ethynylestradiol (EE2), have increasingly negative effects on human and...     

LC-MS-MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters

Alkylphenols (APs), alkylphenol ethoxylates (APEOs), ethoxycarboxylate metabolites (APECs) and bisphenol A were determined in surface water using solid-phase extraction (SPE) followed by triple-quadrupole LC-MS-MS. APs were separated by LC from APECs using an acetonitrile-water-gradient without the addition of any buffer. Nonylphenol ethoxycarboxylates (NPECs) interfere in the detection of nonylphenols (NPs) when using an acidic mobile phase, because they produce the same MS-MS fragment ions (219>133 and 147). 4n-NP shows the characteristic transition 219>106; it is well suited as internal standard. Nonylphenol ethoxylates NPE(n)Os (n=1-17) were analysed separately in a second run by positive ionization using an ammonium acetate mobile phase. Textile industry discharges, the corresponding wastewater treatment plant (WWTP) effluents and the receiving rivers in Belgium and Italy were analysed. Among the substances investigated, NPE1C and NPE2O exhibited the highest concentrations in the water samples, up to 4.5 microg l(-1) NPE1C in a WWTP effluent and 3.6 microg l(-1) NPE2O in a river. The highest NP levels were found in the receiving rivers (max. 2.5 microg l(-1)). The predicted no-effect concentration (PNEC) for NP of 0.33 microg l(-1) for water species was frequently exceeded in the surface waters investigated, suggesting potential adverse effects to the aquatic environment.     

Analysis of 4-nonylphenols, phthalates, and polychlorinated biphenyls in soils and biosolids

When sewage sludge is added to agricultural land, organic chemicals contaminants are also added. The fate of these chemicals, particularly those shown to have oestrogenic potential, has received much research and regulatory interest in recent years. A method was developed for the analysis of 4-nonylphenols, phthalates, and PCB congeners in soils, mesophilic anaerobially digested dewatered (MADD) sewage sludge, and MADD sludge-amended soil. After Soxhlet-extraction, the 4-nonylphenols and phthalates were separated from the PCBs on an isolute cyanopropyl SPE cartridge and analysed by GC-MS directly. The PCBs were acid treated on a Bakerbond PCB-A cartridge, then passed through a gel filtration column of Biobeads SX-3 resin, before GC-MS analysis. The method was successfully validated and then used for routine analysis, where average recoveries of the surrogate standards were 83+/-17% (4-n-heptylphenol), 96+/-11% (dimethyl-tere-phthalate), 101+/-12% (dibenzyl-phthalate), and 79+/-13% (PCBs 6, 54, 104, 155, and 198).     

Effects of 17α-trenbolone and melengestrol acetate on Xenopus laevis growth, development, and survival

The synthetic growth-promoting hormones trenbolone and melengestrol acetate have been detected in the environment near beef cattle feedlots and are reportedly transported via wind-borne particulate matter. Therefore, movement of synthetic hormones from beef cattle feedlots to water bodies via particulate matter is possible. Our objective was to evaluate potential effects of 17α-trenbolone (17α-TB), melengestrol acetate (MGA), and combinations of both on growth, development, and survival of Xenopus laevis larvae. On post-hatch day 2 (stage 33/34), X. laevis larvae were exposed to three nominal concentrations of 17α-TB (10, 100, and 500 ng/L), MGA (1, 10, and 100 ng/L), a combination of both (1/10, 10/100, and 100/500 ng/L MGA/17α-TB), frog embryo teratogenesis assay-Xenopus medium, or a solvent control. Significant increases in all X. laevis growth metrics were observed among larvae in the 1 ng/L MGA?+?10 ng/L 17α-TB and 10 ng/L MGA?+?100 ng/L 17α-TB treatments. Stage of development was increased among larvae in the 1 ng/L MGA?+?10 ng/L 17α-TB treatment group and significantly decreased among those in the 500 ng/L 17α-TB treatment. Total body mass and snout–vent length of X. laevis larvae were significantly reduced in the 100 ng/L MGA and 100 ng/L MGA?+?500 ng/L 17α-TB treatment groups. Larvae exposed to 500 ng/L 17α-TB had decreased total body mass, snout–vent length, and total length. In general, growth measurements decreased with increasing concentration of MGA, 17α-TB, or a combination of both. Survival among all treatments was not significantly different from controls. Amphibians exposed to MGA and 17α-TB in the environment may experience alterations in growth and development.     

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature,pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO(2) (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 gl(-1); while the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure oxygen, an optimal flow rate was observed at 300 ml min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 (+/-0.6) kJ mol(-1).     

Simultaneous quantification of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and pharmaceuticals and personal care products (PPCPs) in Mississippi river water, in New Orleans, Louisiana, USA

An effective analytical method for simultaneously determining 16 polycyclic aromatic hydrocarbons (PAHs), 28 polychlorinated biphenyl (PCBs), and 12 pharmaceuticals and personal care products (PPCPs) has been developed to measure their concentrations in the Mississippi river waters in New Orleans, Louisiana, USA. The method involves the simultaneous extraction of the selected PAHs, PCBs, and PPCPs, from the aqueous phase by solid phase extraction using two-layer disks consisting of C(18) and SDB-XC, and collection of suspended solid in water samples by 0.2-0.6 microm filter in a single step. Target compounds adsorbed on the extraction disks were eluted with methanol, acetone, and dichloromethane. The suspended particles retained by the filter were sonically extracted using the same solvents. GC/MS was used for quantification of PAHs and PCBs directly and of PPCPs after derivatization. The analytical method was used in a 6-month field study of the Mississippi river water for contamination by PAHs, PCBs, and PPCPs and the following concentrations (ng/l) have been obtained: clofibric acid (3.2-26.7), ibuprofen (0-34.0), acetaminophen (24.7-65.2), caffeine (0-38.0), naproxen (0-135.2), triclosan (8.8-26.3), bisphenol A (0-147.2), carbamazepine (42.9-113.7), estrone (0-4.7), 17beta-estradiol (0-4.5), total PAHs (62.9-144.7), and total PCBs (22.2-163.4).     

Estrogens and synthetic androgens in manure slurry from trenbolone acetate/estradiol implanted cattle and in waste-receiving lagoons used for irrigation

The increasing size of concentrated animal feeding operations has led to a concomitant increase in the land-application of manure, which has spawned research on the concentrations and environmental risk assessment of natural and synthetic hormones in animal manures. 17β-Trenbolone acetate (TBA) is widely used in the United States for improving daily gains in beef cattle and is often administered in combination with 17β-estradiol (17β-E2). Trenbolone (TB) and E2 isomers and their metabolites were quantified in manure collection pits and lagoon effluent from beef cattle implanted with the commercial anabolic preparation Ravoler-S (containing 140 mg 17β-trenbolone acetate and 28 mg 17β-E2). Manure pit and lagoon effluent samples were collected weekly for 9 weeks post implanting and analyzed using reverse-phase liquid chromatography tandem mass spectrometry. 17α-TB was the most abundant androgen with the highest concentration observed 2 weeks post implant. 17β-TB and trendione peaked at the end of week 2 and 4, respectively. For the estrogens, the highest concentrations for estrone (E1), estriol (E3), and 17α-E2 were observed after week 4, 6, and 8, respectively. 17β-E2 concentrations were the lowest of the estrogens and erratic over time. In lagoon water, which is used for irrigation, 17α-TB and E1 had the highest detected hormone concentrations (1.53 and 1.72 μg L⁻¹, respectively). Assuming a 1-2 order dilution during transport to surface water, these hormone levels could lead to concentrations in receiving waters that exceed some of the lowest observable effect levels (LOELs) reported for hormones (e.g., 0.01-0.03 μg L⁻¹).     

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 CaCl₂ 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.     

How seasonality affects the flow of estrogens and their conjugates in one of Japan's most populous catchments

A detailed study of the free and conjugated estrogen load discharged by the eight major sewage treatment plants into the Yodo River basin, Japan was carried out. Sampling campaigns were focused on the winter and autumn seasons from 2005 to 2008 and the free estrogens estrone(E1), 17β-estradiol(E2), estriol(E3), 17α-ethynylestradiol(EE2) as well as their conjugated (sulfate and glucuronide) forms. For both sewage effluent and river water E2 and E1 concentrations were greatest during the winter period (December-March). This coincides with the period of lowest rainfall and lowest temperatures in Japan. E1 was the dominant estrogenic component in effluent (means of 10-50 ng/L) followed by E2 (means of 0.5-3 ng/L). The estrogen sulfate conjugates were found intermittently in the 0.5-1.7 ng/L concentration range in the sewage effluents. The greatest estrogen exposure was found to be in the Katsura River tributary which exceeded 1 ng/L E2-equivalents during the winter period.     

Determination of Source Contributions to Ambient PM2.5 in Kaohsiung,Taiwan, Using a Receptor Model

ABSTRACT

Ambient particulates of PM_2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM_2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM_2.5.

The mean concentration of ambient PM_2.5 was 42.6953.68 μj.g/m³ for the sampling period. The abundant species in ambient PM_2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO₄ ^2- (12.8-15.1%), NO₃ ^- (8.110.3%), NH₄+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM_2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO₄ ^2- and NO₃ ^-), and outdoor burning of agriculture wastes (13-17%).     

Spatial distribution and vertical profile of polybrominated diphenyl ethers and hexabromocyclododecanes in sediment core from Tokyo Bay, Japan

Brominated flame retardants (BFRs), hexabromocyclododecanes (HBCDs) and polybrominated diethyl ethers (PBDEs) were detected in three sediment cores and six surface sediments of Tokyo Bay, Japan. HBCDs were detected for the first time in this region with concentrations ranging from 0.056 to 2.3 ng/g dry wt, implying their widespread contamination, even though their concentrations were lower than summation operatorPBDEs (di- to nona-BDEs) and BDE-209. Levels of these compounds were higher near to the highly populated industrial area of the bay implicating industrial and human activities as sources of these compounds. Summation operatorPBDEs increased in the sediment layer up to the mid-1990s and decreased afterwards, whereas BDE-209 showed an increasing trend until now, following the usage of different commercial BDE mixtures. HBCDs first appeared in the mid-1970s and increased until today. The annual surficial flux of HBCDs (0.62-2.4 ng/cm2/yr) is equal to summation operatorPBDEs (0.95-2.6 ng/cm2/yr) but lower than that of BDE-209 (17-58 ng/cm2/yr).