Factors Affecting Behavior of Phenolic Endocrine Disruptors, Estrone and Estradiol, in Constructed Wetlands for Domestic Sewage Treatment.

This study investigated the efficiency of 12 pilot-scale constructed wetlands (CWs) with different configurations on the removal of estrone and estradiol from raw domestic sewage. An orthogonal design was employed to evaluate the impact of four principal design parameters of CWs, including four wetland types, three substrates, three plant conditions, and three hydraulic loading rates, in summer and winter. A bench-scale anoxic simulation test was performed in the laboratory to clarify the photolysis, sorption, and degradation of estrogens. Estrogens were more effectively removed by the 12 CWs during summer. The experiment showed that target estrogens were efficiently removed by wetland substrate under anoxic conditions through exothermic sorption and degradation even in winter. This suggests that the inefficient removal in CWs in winter likely resulted from subsequent cleavage of a considerable amount of estrogen conjugates in influent due to insufficient decomposition at low temperatures. The transformation from estradiol to estrone could be driven by residual microbial activities not inhibited by azide, and the reversible process was then driven by active microorganisms but not solely abiotic redox reactions. Among the four design parameters, wetland-type was the most important and downward-vertical flow CWs performed best.

[Removal Behavior of Ibuprofen and Diclofenac in Different Constructed Wetlands].

Ibuprofen and diclofenac, two commonly used pharmaceuticals, were studied to evaluate the removal behavior of acid pharmaceuticals in constructed wetlands (CWs) with different flow types, vegetation and seasons. It was shown that flow types influenced the results significantly. The average removal efficiency of ibuprofen in horizontal subsurface flow (HSSF) and vertical subsurface flow (VSSF) CWs (69% and 60%, respectively) was significantly higher than that in surface flow (SF) CWs (26%). For diclofenac, SF CWs (58%) was significantly higher than HSSF and VSSF CWs (49% and 43%, respectively). In addition, the presence of plants improved the efficiency of ibuprofen, while it had no significant influence on the removal of diclofenac. Paired t-test found out that summer and autumn season variety had little impact on the removal. Furthermore, the removal of diclofenac and DO, as well as COD, showed very significant negative correlations. Opposite to diclofenac, the removal of ibuprofen had good positive correlations with dehydrogenase activities. The research indicated that aerobic biodegradation behavior mainly took place in ibuprofen, yet anaerobic biodegradation and photolysis behavior were expected for diclofenac.

Contrasting effects of silicates on cadmium uptake by three dicotyledonous crops grown in contaminated soil.

The effects of several silicates (talcum powder (TP), calcium silicate (CS), sodium silicate (SS), and potassium silicate (PS)), in comparison with other amendments (quicklime (QL) and potassium dihydrogen phosphate (PDP)) on cadmium (Cd) uptake by three dicotyledonous crops (Amaranthus hypochondriacus L. Cv. 'K112', Amaranthus tricolor L., and Brassica oleracea var. albiflora Kuntze) were investigated in Cd-contaminated soil. The effects of both application methods of amendments (singly and combined) and timing of application were also evaluated. Sodium silicate was the most effective in reducing crop Cd uptake and translocation, which was diminished by 51% in roots, 53% in stems, and 72% in leaves on average. Application of CS amendment showed greater efficiency than PDP amendment in decreasing Cd uptake by crops and resulted in increased biomass. Potassium silicate only slightly decreased shoot Cd concentration. Combination of PDP and SS was able to overcome the inhibitory effect of SS on crop yield while decreasing Cd concentrations in roots, stems and leaves of the tested crops by average rates of 52, 65, and 68% respectively. Applications of SS and PS significantly reduced the root-to-shoot Cd transfer factor. We found that Si accumulation in crops was not associated with lower Cd concentration, indicating that Si in crops may play a major role in alleviating metal stress rather than inhibiting crop Cd accumulation. We suggested that the inhibitive effect of silicates on crops Cd uptake was majorly attributed to the properties of the silicates, those were their specific effects on soil pH and cations, which increased Cd adsorption by soil and suppressed Cd uptake from soil solution by increasing the relative dissolved concentrations of competing cations.

[Transfer characteristics of cadmium in soil-vegetable-insect food chain].

Taking two kinds of vegetables (Brassica rapa and Amaranthus mangostanus) and one insect species (Prodenia litura) as test materials, a greenhouse pot experiment was conducted to study the transfer characteristics of cadmium (Cd) in soil-vegetable-insect food chain and the distribution patters of different Cd chemical forms in the organs of the two vegetables. With the increasing concentration of applied Cd in soil, the biomass of the two vegetables decreased significantly, while the Cd concentration in the vegetables had a significant increase. The Cd concentration in the vegetable organs decreased in the order of stem > root > leaf for A. mangostanus, and of stem > leaf > root for B. rapa. The Cd concentration in P. litura larvae also increased with the increasing concentration of Cd in soil, and the maximum Cd concentration in the P. litura larvae on B. rapa and A. mangostanus was 36.7 and 46.3 mg x kg(-1), respectively. In the feces of the larvae on B. rapa and A. mangostanus, the Cd concentration was up to 190 and 229.8 mg x kg(-1), respectively, suggesting that the most part of Cd absorbed by P. litura larvae was excreted out of their bodies via feces. In the organs of the two vegetables, NaCl-extractable Cd was the dominant Cd form (> 70%), followed by d-H2O- and ethanol-extractable Cd, while the HAc-extractable Cd (insoluble cadmium phosphate), HCl-extractable Cd (insoluble cadmium oxalate), and residual Cd only had a very low concentration. Such a present pattern of different Cd forms in vegetable organs could be conducive to the Cd transfer in the food chain. P. litura could ease Cd poison by excreting large amount of absorbed Cd via feces, and effectively restrict the transfer of Cd to next trophic level. Since B. rapa and A. mangostanus could accumulate large amount of Cd in their biomass, the two vegetables were suggested not to be planted in highly Cd-contaminated soil.

[Concentrations and distribution of tetracycline antibiotics in vegetable field soil chronically fertilized with manures].

Occurrence of antibiotics in the soils substantially fertilized with antibiotics-enriched animal manures is very of concern. This paper investigated the concentration and distribution of four tetracycline antibiotics in soils from vegetable field chronically fertilized with manures in subtropical area using solid-phase extraction followed by high-performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-MS/MS). The sum concentrations of four tetracycline compounds ranged from 1.35 microg/kg to 22.52 microg/kg with an average of 7.35 microg/kg. There were thirty one to one hundred percent of the soil samples were detected with average concentrations of 0.63- 3.11 microg/kg for four tetracycline compounds which dominated mostly with oxytetracycline and secondly with deoxytetracycline. Composition and levels of tetracycline compounds varied obviously in both horizontal and vertical soils. The concentration of tetracycline compounds in soil profile decreased rapidly with the depth and some of the compounds were still detected in 60 to 80 centimeter depth of soil. It is concluded that tetracycline antibiotics in soils from vegetable field chronically fertilized with manures in subtropical area were generally lower and less ecotoxic risk for soil ecosystem. But it should not be ignored in view of combined toxic effect and resistance of various compounds.

[Occurrence of quinolone and sulfonamide antibiotics in swine and cattle manures from large-scale feeding operations of Guangdong Province].

The occurrence and distribution of four quinolones and four sulfonamides in swine and cattle feces sampled from twenty large-scale feeding operations in different areas of Guangdong province were detected using solid phase extraction (SPE) and high performance liquid chromatography (HPLC). Quinolone and sulfonamide compounds were observed in all pig dung samples. Their total concentrations ranged from 24.5 microg/kg to 1516.2 microg/kg (F. W.) with an average of 581.0 microg/kg and ranged from 1925.9-13399.5 microg/kg with an average of 4403.9 microg/kg respectively. The dominant compounds in pig feces were ciprofloxacin and enrofloxacin for quinolones and sulfamerazine and sulfamethoxazole for sulfonamides. Quinolone compounds which dominated with norfloxacin and ciprofloxacin were also observed in all cattle dung samples, its total concentrations ranged from 73.2 microg/kg to 1328.0 microg/kg which averaged 572.9 microg/kg. While the positive rates of sulfonamide compounds detected in cattle dung samples were above 90%, predominated by sulfamethoxazole and sulfamerazine. Concentration and distribution of both quinolone and sulfonamide compounds in swine and cattle dungs of different feeding operations varied greatly. Relatively high concentrations of the two kinds of antibiotics were found in both swine and cattle dungs from Guangzhou area, while sulfameter and sulfamethazine in cattle dungs from Foshan and Shenzhen areas were below the limit of detection.

Investigation of sulfonamide, tetracycline, and quinolone antibiotics in vegetable farmland soil in the Pearl River Delta area, southern China.

Thirteen antibiotics in soil from vegetable farmlands of the Pearl River Delta, southern China, were investigated. At least three antibiotics were detected in each sample. Six antibiotics including four quinolones, tetracycline, and sulfamethoxazole were detected in >94% of the samples. The total contents of three tetracyclines, eight sulfonamides, and four quinolones were not detected-242.6, 33.3-321.4, and 27.8-1537.4 µg/kg, respectively. The highest antibiotic concentrations were observed mainly in vegetable farmlands affiliated with livestock farms. Chlortetracycline, sulfameter, and quinolones in some samples exceed the ecotoxic effect trigger value (100 µg/kg) set by the Steering Committee of Veterinary International Committee on Harmonization. The composition and concentration of antibiotics in soil were correlated with vegetable species. This study has revealed an alarming condition of antibiotics in vegetable farmland soil. Further investigation including environmental fate, plant uptake, and human exposure to antibiotics by plant-derived food should be conducted.

Determination of four fluoroquinolone antibiotics in tap water in Guangzhou and Macao.

Four fluoroquinolone antibiotics (norfloxacin, ciprofloxacin, lomefloxacin, and enrofloxacin) in tap water in Guangzhou and Macao were analyzed using high performance liquid chromatography fluorescence detection. The results showed that all target antibiotics were detected in high rate both in Guangzhou (77.5%) and Macao (100%), ranging from 1.0 to 679.7 ng/L (SD

[Preliminary study on occurrence and health risk assessment of quinolone antibiotics in vegetables from Guangzhou, China].

Quinolone antibiotics (QNs) including norfloxacin (NOR), enrofolxacin (ENR), ciprofloxacin (CIP) and lomefloxacin (LOM) in vegetable samples collected from Guangzhou were determined by high performance liquid chromatography (HPLC) coupled with fluorescent detector (FLD). The detected frequency of QNs was 96% in vegetables. The total concentration of quinolones (sigma QNs) detected in vegetable ranged from 1.0 microg/kg to 1 683.1 microg/kg (F.W.). Leafy vegetable topped the content of quinolones among the three types of vegetables, followed by the melon-fruit vegetable and rhizome vegetable. The detected frequency of the four quinolone antibiotics ranked as NOR > CIP > LOM > ENR. Except ENR, concentrations of CIP, NOR, LOM and sigma QNs in pollution-free vegetable, green vegetable and organic vegetable were higher than those in routine cultivated vegetables. The maximum contribution to ADI value (caculated by the sum of CIP and ENR) is estimated up to 41.5% and 83% for adults and children respectively via consumption of vegetables.

[Investigation of sulfonamides and tetracyclines antibiotics in soils from various vegetable fields].

The occurrence and distribution of 9 selected antibiotics, that involved with oxytetracycline (OTC), tetracycline (TC), chlortetracycline (CTC), sulfamethazine (SM2), sulfadiazine (SDZ), sulfamerazine (SMR), sulfameter, (SMT), sulfamethoxazole (SMZ) and sulfadimethoxine (SDM), were screened at 14 typical vegetable fields located in Shenzhen, Guangzhou, Huizhou, Dongguan regions,with high-performance liquid chromatography (HPLC). Data showed that almost all soil samples were unavoidably contaminated with antibiotics. The sum concentration of 3 tetracyclines (TCs) and 6 sulfonamides (SAs) in soils ranged from undetected to 242.6 microg/kg and 33.3 to 321.4 microg/kg respectively, while the medium concentrations were 84.8 microg/kg of tetracyclines and 121 microg/kg of sulfonamides. The individual detectable probability of the two groups of antibiotics ranged from 19.35% to 96.77% (TCs) and from 25.81% to 93.50% (SAs). TC, SMZ, SMT and SM2 were more abundant in soil among the selected antibiotics. The study also suggested that the total amount of both TCs and SAs in different vegetable fields ranked as hoggery vegetable field > non-pollution vegetable field > routine vegetable field > greenfood vegetable field, and there should exist some relationship between vegetable planting and antibiotics amount in soil which was related to different fertilization, irrigation and vegetable species. The concentrations of the selected antibiotics are comparable to those reported from the other countries in the world, but the detectable probability of the antibiotics in our study site is higher than that from the reference data. More attention should be paid to antibiotics pollution of soil in vegetable fields.