Investigation of free and conjugated estrogen fate and emission coefficients in three duck farms.

Concentration animal feeding operation (CAFO) is an important source of environmental estrogen. However, to the best of our knowledge, the data on estrogen discharge during duck breeding and growth is insufficient. This study used liquid chromatography with tandem mass spectrometry (LC/MS/MS) to analyze the free and conjugated estrogen concentrations in the surface water, outlet water, groundwater, and duck manure/soil mixture at three duck farms in Taiwan. Natural estrogen species included estrone (E1), 17ß-estradiol (E2), estriol (E3), estrone-3-sulfate (E1-3S), 17ß-estradiol-3-sulfate (E2-3S), estrone-3-glucuronide (E1-3G), and 17ß-estradiol-3-glucuronide (E2-3G), whereas synthetic estrogen included 17α-ethynylestradiol (EE2) and diethylstilbestrol (DES). This study showed that the total estrogen concentrations in the surface water and groundwater were 15.4 and 4.5 ng/L, respectively, which constituted 56% and 58%, respectively, conjugated estrogen. From the pond to the outlet water, the total estrogen concentration decreased by 3.9 ng/L (23% loss) in the duck farms. However, the estrogenic potency was slightly reduced from 0.91 to 0.88 E2 equivalent/L, showing a negligible decrease. From the pond to the outlet water, the field results showed that converting the conjugated estrogen into free estrogen in the duck farm-released water increased their environmental hazard. Primarily E1, with an average concentration of 0.9 ± 1.6 ng/g, was present in the duck manure. The estrogen excreted by the ducks in the pond (from surface water to outlet water) was estimated to be 0.18 kg/million head-year. Although the estrogen concentration in the duck farms was low, the environmental impact of CAFO should not be neglected.

Combination of a fast cleanup procedure and a DR-CALUX® bioassay for dioxin surveillance in Taiwanese soils.

Our goal was to determine dioxin levels in 800 soil samples collected from Taiwan. An in vitro DR-CALUX® assay was carried out with the help of an automated Soxhlet system and fast cleanup column. The mean dioxin level of 800 soil samples was 36.0 pg-bioanalytical equivalents (BEQs)/g dry weight (d.w.). Soil dioxin-BEQs were higher in northern Taiwan (61.8 pg-BEQ/g d.w.) than in central, southern, and eastern Taiwan (22.2, 24.9, and 7.80 pg-BEQ/g d.w., respectively). Analysis of multiple linear regression models identified four major predictors of dioxin-BEQs including soil sampling location (ß = 0.097, p < 0.001), land use (ß = 0.065, p < 0.001), soil brightness (ß = 0.170, p < 0.001), and soil moisture (ß = 0.051, p = 0.020), with adjusted R2 = 0.947 (p < 0.001) (n = 662). An univariate logistic regression analysis with the cut-off point of 33.4 pg-BEQ/g d.w. showed significant odds ratios (ORs) for soil sampling location (OR = 2.43, p < 0.001), land use (OR = 1.47, p < 0.001), and soil brightness (OR = 2.83, p = 0.009). In conclusion, four variables, including soil sampling location, land use, soil brightness, and soil moisture, may be related to soil-dioxin contamination. Soil samples collected in northern Taiwan, and especially in Bade City, soils near industrial areas, and soils with darker color may contain higher dioxin-BEQ levels.

Estrogen degradation and sorption onto colloids in a constructed wetland with different hydraulic retention times.

Endocrine disrupting compounds are a global concern, owing to their interference with the endocrine system of wildlife. In particular, natural estrogens at concentrations as low as ng/L level can interrupt the endocrine system of many organisms. A constructed wetland is an effective means of removing the residual levels of estrogen. This study investigates the estrogen degradation and sorption on colloids in a constructed wetland at hydraulic retention times (HRTs) of 27.5, 45.9, and 137.5h. Three natural estrogens (i.e. estrone (E1), 17ß-estradiol (E2), and estriol (E3)) are analyzed with liquid chromatography/tandem mass spectrometry. At HRT=27.5h, no degradation occurs; at HRT=45.9h, the degradation rates are 0-46.2%; and at HRT=137.5h, the degradation rates are 40-84.3%. Additionally, estrogen sorption coefficients (logKCOC values) range from 3.37 to 4.89. Average logKCOC values are 4.08±0.33, 4.04±0.34, and 4.11±0.28 for E1, E2, and E3, respectively. At different HRTs, values of logKCOC increase with an increasing HRT. Analytical results indicate that constructed wetlands can remove residual natural estrogens. With an increasing HRT, the estrogen degradation rate increases as well as the estrogen sorption on colloids.

An improved AhR reporter gene assay for analyzing dioxins in soil, sediment and fish.

Our goal was to develop a fast-screening bioassay to determine dioxin levels in the environmental and biological samples from dioxin-contaminated areas. Our original dioxin-responsive-element (DRE)-driven luciferase bioassay (using Huh7-DRE-Luc cells) was modified by reducing the incubation temperature of the cell culture from 37 to 35°C and by adding phorbol-12-myristate-13-acetate, and the modified bioassay was used to examine samples from soil, sediment, and fish. The results of this bioassay were shown to be significantly related to those of the high-resolution gas chromatography/high-resolution mass spectrometry assay of dioxins. The correlative equation was: log (PCDD/Fs I-TEQs) = 1.19 × log (BEQs) - 1.15 with R(2) = 0.95 (p < 0.001).

High estrogen concentrations in receiving river discharge from a concentrated livestock feedlot.

Environmental estrogenic chemicals interrupt endocrine systems and generate reproductive abnormalities in wildlife, especially natural and synthetic estrogenic steroid hormones such as 17beta-estradiol (E2), estrone (E1), estriol (E3), 17alpha-ethynylestradiol (EE2), and diethylstilbestrol (DES). Concentrated animal feedlot operations (CAFOs) are of particular concern since large amounts of naturally excreted estrogens are discharged into aquatic environments. This study investigated E2, E1, E3, EE2, and DES with high performance liquid chromatography/tandem mass (HPLC-MS/MS) analyses along Wulo Creek in southern Taiwan, near a concentrated livestock feedlot containing 1,030,000 broiler chickens, 934,000 laying hens, 85,000 pigs, and 1500 cattle. Sampling was performed from December 2008 to May 2009, in which 54 samples were collected. Experimental results indicate that concentrations of EE2 were lower than the limit of detection (LOD), and concentrations of DES were only detected twice. Concentrations ranged from 7.4 to 1267 ng/L for E1, from not detected (ND) to 313.6 ng/L for E2, and from ND to 210 ng/L for E3. E1 had the highest average mass fraction (72.2 + or - 3.6%), which was significantly higher than E3 (16.2 + or - 1.7%) and E2 (11.5 + or - 2.6%). Additionally, the mean E2 equivalent quotient (EEQ) ranged from 17.3 to 137.9 ng-E2/L. Despite having a markedly lower concentration than E1, E2 more significantly contributed (52.4 + or - 6.0%) EEQ than E1 (19.7 + or - 3.5%). Moreover, the concentrations of E2, E1, and E3 upstream were significantly higher than concentrations downstream, suggesting a high attenuation effect and fast degradation in the study water. Most concentrations in winter season were higher than those of spring season due to the low dilution effect and low microbial activity in the winter season. Based on the results of this study, we recommend further treatment of the wastewater discharge from the feedlot.

Regeneration of Ce(IV) in simulated spent Cr-etching solutions using an undivided cell.

This study investigated regeneration of Ce(IV) from Ce(III) oxidation at 0.05-0.5Acm(-2) in 4M HNO(3) with/without anion impurities (SO(4)(2-) (0.01-0.2M), Cl(-) (0.01-0.08M), and/or Cr(2)O(7)(2-) (0.005-0.016M)) in an undivided cell. Both Ce(IV) yield and current efficiency (CE) were significantly lower in 0.1M than in 1-4M HNO(3) and different on anode materials (in order Pt>IrO(2)/Ti>glassy carbon). The apparent rate constants for Ce(III) oxidation on the Pt anode (k(1)) and for Ce(IV) reduction on a stainless steel cathode (k(2)) were (0.40-1.80)x10(-4) and (0.08-1.01)x10(-4)s(-1), respectively, corresponding to the apparent mass transfer coefficients of (2.0-9.0)x10(-3) and (0.4-5.1)x10(-3)cms(-1), respectively. For Ce(III) oxidation at 0.3Acm(-2) in 4M HNO(3) containing multi-impurity (0.025M SO(4)(2-)+0.08M Cl(-)+0.016M Cr(2)O(7)(2-)), the k(1) was lowered by one order of magnitude although the k(2) remained unchanged, and both Ce(IV) yield and CE were reduced by approximately 89%. The decrease of Ce(IV) yield and CE by the uni-impurity was in order Cl(-)>Cr(2)O(7)(2-)>SO(4)(2-). The obtained parameters are useful to design undivided batch reactors for the Ce(IV) electro-regeneration in spent Cr-etching solutions.

Anion effects on the electrochemical regeneration of Ce(IV) in nitric acid used for etching chromium.

The anion impurities such as SO4(2-), Cl(-), and Cr2O7(2-) commonly present in the spent (hazardous) Cr-etch solutions from color filter manufacturing processes may influence the solutions' regeneration by the electrooxidation of Ce(III) to Ce(IV). This study, therefore, investigated the effects of these anions on Ce(III)/Ce(IV) redox reactions at glassy carbon in HNO3. In cyclic voltammetric tests, the presence of SO4(2-) decreased the formal potential but increased the peak potential separation (Delta Ep) of Ce(III)/Ce(IV) couple, and lowered the peak current for Ce(IV) reduction whereas Cl(-) did not change the formal potential and Delta Ep, but the peaks for Cl(-) and Ce(III) oxidation partially overlapped. Cr2O7(2-) slightly lowered the peak current for Ce(III) oxidation but significantly decreased that for Ce(IV) reduction. The Tafel slope for Ce(III) oxidation was approximately 65mVdecade(-1) in the absence of anion impurities. Increasing SO4(2-), Cl(-), or Cr2O7(2-) in solution raised the Tafel slope. The Ce(III)/Ce(IV) equilibrium potential decreased with the increase of SO4(2-) or Cl(-) but was hardly influenced by Cr2O7(2-) addition. These observations from individual anion species together well explained the anions' co-effect (kinetic hindrance) on the Ce(III) oxidation in HNO3, revealing that these anions are unfavorable for the electrooxidation of Ce(III) in the spent Cr-etch solutions.