Selected personal care products and endocrine disruptors in biosolids: an Australia-wide survey

Personal care products (PCPs) and endocrine disrupting compounds (EDCs) are groups of organic contaminants that have been detected in biosolids around the world. There is a shortage of data on these types on compounds in Australian biosolids, making it difficult to gain an understanding of their potential risks in the environment following land application. In this study, 14 biosolids samples were collected from 13 Australian wastewater treatment plants (WWTPs) to determine concentrations of eight compounds that are PCPs and/or EDCs: 4-t-octylphenol (4tOP), 4-nonylphenol (4NP), triclosan (TCS), bisphenol A (BPA), estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2). Concentration data were evaluated to determine if there were any differences between samples that had undergone anaerobic or aerobic treatment. The concentration data were also compared to other Australian and international data. Only 4tOP, 4NP, TCS, and BPA were detected in all samples and E1 was detected in four of the 14 samples. Their concentrations ranged from 0.05 to 3.08 mg/kg, 0.35 to 513 mg/kg, < 0.01 to 11.2 mg/kg, < 0.01 to 1.47 mg/kg and < 45 to 370 μg/kg, respectively. The samples that were obtained from WWTPs that used predominantly anaerobic treatment showed significantly higher concentrations of the compounds than those obtained from WWTPs that used aerobic treatment. Overall, 4NP, TCS and BPA concentrations in Australian biosolids were lower than global averages (by 42%, 12% and 62%, respectively) and 4tOP concentrations were higher (by 25%), however, of these differences only that for BPA was statistically significant. The European Union limit value for NP in biosolids is 50 mg/kg, which 4 of the 14 samples in this study exceeded.     

Microbial and antibiotic resistant constituents associated with biological aerosols and poultry litter within a commercial poultry house

Poultry are known to harbor antibiotic resistant and pathogenic bacteria, and as such poultry litter and poultry house air can be contaminated with these bacteria. However, the presence of antibiotic resistant bacteria in biological aerosols and litter is largely not understood. The purpose of this study was to determine the amount of aerosolized bacteria and endotoxin, particularly fecal indicators, staphylococci, and enterococci, associated with poultry house and outdoor air. Aerosol samples were collected at multiple locations on the farm and in the house. Antibiotic resistance was investigated using the Kirby Bauer method on selected isolates using twelve different antibiotics spanning both narrow to broad spectrums of effectiveness. Overall there was a cyclical increase in bacterial concentrations as flocks progressed from pre-flock to late-flock, with > 2 orders magnitude lower concentration during pre-flock periods (no chickens), in both the litter and aerosol samples. The house environment provided for significantly concentrated bacterial and endotoxin levels. It was estimated that Staphylococcus bacteria accounted for at least 90% of cultured aerobic bacteria and culture-independent 16S rRNA analyses demonstrated that significant population changes occurred from pre- to late-flock. Rarely was an isolate resistant to more than 4 antibiotic classes; however there was a trend upwards in overall resistance of enterococci as the flock cycle progressed. It appears that although levels of antibiotic resistant bacteria were highly concentrated within the house, levels were much lower outside of the house, and very little house escape occurred.     

Fate of steroid hormones and endocrine activities in swine manure disposal and treatment facilities

Manure may contain high concern endocrine-disrupting compounds (EDCs) such as steroid hormones, naturally produced by pigs, which are present at μg L⁻¹ levels. Manure may also contain other EDCs such as nonylphenols (NP), polycyclic aromatic hydrocarbons (PAHs) and dioxins. Thus, once manure is applied to the land as soil fertilizer these compounds may reach aquifers and consequently living organisms, inducing abnormal endocrine responses. In France, manure is generally stored in anaerobic tanks prior spreading on land; when nitrogen removal is requested, manure is treated by aerobic processes before spreading. However, little is known about the fate of hormones and multiple endocrine-disrupting activities in such manure disposal and treatment systems. Here, we determined the fate of hormones and diverse endocrine activities during manure storage and treatment by combining chemical analysis and in vitro quantification of estrogen (ER), aryl hydrocarbon (AhR), androgen (AR), pregnane-X (PXR) and peroxysome proliferator-activated γ (PPARγ) receptor-mediated activities. Our results show that manure contains large quantities of hormones and activates ER and AhR, two of the nuclear receptors studied. Most of these endocrine activities were found in the solid fraction of manure and appeared to be induced mainly by hormones and other unidentified pollutants. Hormones, ER and AhR activities found in manure were poorly removed during manure storage but were efficiently removed by aerobic treatment of manure.     

Impact of biosolids on the persistence and dissipation pathways of triclosan and triclocarban in an agricultural soil

The broad spectrum antimicrobial agents triclosan (TCS) and triclocarban (TCC) are widely used in many personal care products. Knowledge concerning the fate of these two compounds in different environmental matrices is scarce. In this study, the fate of TCS and TCC in soil following direct addition, or when residues were applied via either liquid municipal biosolids (LMB) or dewatered municipal biosolids (DMB) was investigated in laboratory dissipation experiments and under outdoor conditions using radioisotope methods. In laboratory incubations, ¹⁴C-TCC or ¹⁴C-TCS was added to microcosms containing a loam soil and the rate of ¹⁴CO₂ accumulation and loss of solvent-extractable ¹⁴C were determined during incubation at 30 °C. Compared to when TCC or TCS was added directly to soil, both chemicals were mineralized more rapidly when applied in LMB, and both were mineralized more slowly when applied in DMB. The application matrix had no effect on the rate of removal of extractable residues. In field experiments, parent compounds were incorporated directly in soil, incorporated via LMB, or a single aggregate of amended DMB was applied to the soil surface. During the experiment soil temperatures ranged from 20 °C to 10 °C. Dissipation was much slower in the field than in the laboratory experiments. Removal of non-extractable residues was faster in the presence of LMB than the other treatments. Recovery of extractable and non-extractable residues suggested that there was little atmospheric loss of ¹⁴C. Triclocarban readily formed non-extractable residues with DMB whereas TCS did not. Overall, this study has identified that both the pathways and the kinetics of TCS and TCC dissipation in soil are different when the chemicals are carried in biosolids compared to when these chemicals are added directly to the soil.     

Polybrominated diphenyl ethers in sewage sludge and treated biosolids: Effect factors and mass balance

Polybrominated diphenyl ether (PBDE) flame retardants have been consistently detected in sewage sludge and treated biosolids. Two hundred and eighty-eight samples including primary sludge (PS), waste biological sludge (WBS) and treated biosolids from fifteen wastewater treatment plants (WWTPs) in Canada were analyzed to investigate the factors affecting accumulation of PBDEs in sludge and biosolids. Factors examined included environmental/sewershed conditions and operational parameters of the WWTPs. PBDE concentrations in PS, WBS and treated biosolids were 230–82,000 ng/g, 530–8800 ng/g and 420–6000 ng/g, respectively; BDE-209,-99, and -47 were the predominant congeners. Concentrations were influenced by industrial input, leachate, and temperature. Several examinations including the measurement of BDE-202 indicated minimal debromination during wastewater treatment. Estimated solids-liquid distribution coefficients were moderately correlated to hydraulic retention time, solids loading rate, mixed liquor suspended solids, solids retention time, and removal of organic solids, indicating that PBDE partitioning to solids can be optimized by WWTPs' operational conditions. Solids treatment type strongly affected PBDE levels in biosolids: 1.5 times increase after solids digestion, therefore, digestion efficiency could be a potential factor for variability of PBDEs concentration. In contrast, alkaline treatment reduced PBDE concentrations in biosolids. Overall, mass balance approaches confirmed that PBDEs were removed from the liquid stream through partitioning to solids. Variability of PBDE levels in biosolids could result in different PBDEs burdens to agricultural land, and different exposure levels to soil organisms.     

Pharmaceutical and personal care products in tile drainage following land application of municipal biosolids

Land application of municipal biosolids (sewage) is a common farming practice in many parts of the world. There is potential for transport of pharmaceuticals and personal care products (PPCPs) from agricultural fields to adjacent surface waters via tile drainage systems. In this study, liquid municipal biosolids (LMB) (total solids=11,933 mg L(-1)), supplemented with selected PPCPs and the fluorescent dye tracer rhodamine WT (RWT), were applied to tile drained fields using two land application approaches. Objectives included evaluating the relative benefits of land application practices with respect to reducing PPCP loadings to tile drains, evaluating PPCP persistence in tile water, and determining whether rhodamine WT can be used to estimate PPCP mass loads in tile. The PPCPs examined included an antibacterial agent used in personal care products (triclosan), a metabolite of nicotine (cotinine), and a variety of drugs including two sulfonamide antimicrobials (sulfapyridine, sulfamethoxazole), a beta-blocker (atenolol), an anti-epileptic (carbamazepine), an antidepressant (fluoxetine), analgesic/anti-inflammatories (acetaminophen, naproxen, ibuprofen), and a lipid-regulator (gemfibrozil). Maximum observed PPCP concentrations in the spiked LMB were about 10(3) ng g(-1) dry weight. PPCPs were shown to move rapidly via soil macropores to tile drains within minutes of the land application. Maximum observed PPCP concentrations in tile effluent associated with the LMB application-induced tile flow event were approximately 10(1) to 10(3) ng L(-1). PPCP mass loads, for the application-induced tile-hydrograph event, were significantly (p<0.1) higher for surface spreading over non-tilled soil (incorporation tillage occurring 20 h post-application), relative to aerating soil immediately prior to surface spreading using an AerWay slurry deposition system. PPCP concentrations that were detected above the limit of quantitation (LOQ) in tile water during several precipitation-induced tile flow events that occurred post-application, included: triclosan (max. approximately 1.5 x 10(2) ng L(-1)), carbamazepine (max. approximately 7 x 10(1) ng L(-1)), atenolol (max approximately 4 x 10(1) ng L(-1)), and cotinine (max approximately 2 x 10(1) ng L(-1)). In spite of their presence in biosolids, the other PPCPs were not observed above LOQ concentrations during these events. PPCP concentrations were predicted from RWT concentrations over a 40 day study period. Tile mass loads as a percent of PPCP mass applied to soil ranged from 4.2%+/-SD of 9.2% to 7.1%+/-10.9% for the AerWay system and surface spreading plus incorporation treatments, respectively.     

The effect of thermal hydrolysis pretreatment on the anaerobic degradation of nonylphenol and short-chain nonylphenol ethoxylates in digested biosolids

The presence of micropollutants can be a concern for land application of biosolids. Of particular interest are nonylphenol diethoxylate (NP₂EO), nonylphenol monoethoxylate (NP₁EO), and nonylphenol (NP), collectively referred to as NPE, which accumulate in anaerobically digested biosolids and are subject to regulation based on the environmental risks associated with them. Because biosolids are a valuable nutrient resource, it is essential that we understand how various treatment processes impact the fate of NPE in biosolids. Thermal hydrolysis (TH) coupled with mesophilic anaerobic digestion (MAD) is an advanced digestion process that destroys pathogens in biosolids and increases methane yields and volatile solids destruction. We investigated the impact of thermal hydrolysis pretreatment on the subsequent biodegradation of NPE in digested biosolids. Biosolids were treated with TH, anaerobic digestion, and aerobic digestion in laboratory-scale reactors, and NPE were analyzed in the influent and effluent of the digesters. NP₂EO and NP₁EO have been observed to degrade to the more estrogenic NP under anaerobic conditions; therefore, changes in the ratio of NP:NPE were of interest. The increase in NP:NPE following MAD was 56%; the average increase of this ratio in four sets of TH-MAD samples, however, was only 24.6 ± 3.1%. In addition, TH experiments performed in pure water verified that, during TH, the high temperature and pressure alone did not directly destroy NPE; TH experiments with NP added to sludge also showed that NP was not destroyed by the high temperature and pressure of TH when in a more complex sludge matrix. The post-aerobic digestion phases removed NPE, regardless of whether TH pretreatment occurred. This research indicates that changes in biosolids processing can have impacts beyond just gas production and solids destruction.     

Release of antibiotic resistant bacteria and genes in the effluent and biosolids of five wastewater utilities in Michigan

The purpose of this study was to quantify the occurrence and release of antibiotic resistant genes (ARGs) and antibiotic resistant bacteria (ARB) into the environment through the effluent and biosolids of different wastewater treatment utilities including an MBR (Membrane Biological Reactor) utility, conventional utilities (Activated Sludge, Oxidative Ditch and Rotatory Biological Contactors-RBCs) and multiple sludge treatment processes (Dewatering, Gravity Thickening, Anaerobic Digestion and Lime Stabilization). Samples of raw wastewater, pre- and post-disinfected effluents, and biosolids were monitored for tetracycline resistant genes (tetW and tetO) and sulfonamide resistant gene (Sul-I) and tetracycline and sulfonamide resistant bacteria. ARGs and ARB concentrations in the final effluent were found to be in the range of ND(non-detectable)-2.33 × 10⁶ copies/100 mL and 5.00 × 10²-6.10 × 10⁵ CFU/100 mL respectively. Concentrations of ARGs (tetW and tetO) and 16s rRNA gene in the MBR effluent were observed to be 1-3 log less, compared to conventional treatment utilities. Significantly higher removals of ARGs and ARB were observed in the MBR facility (range of removal: 2.57-7.06 logs) compared to that in conventional treatment plants (range of removal: 2.37-4.56 logs) (p < 0.05). Disinfection (Chlorination and UV) processes did not contribute in significant reduction of ARGs and ARB (p > 0.05). In biosolids, ARGs and ARB concentrations were found to be in the range of 5.61 × 10⁶-4.32 × 10⁹ copies/g and 3.17 × 10⁴-1.85 × 10⁹ CFU/g, respectively. Significant differences (p < 0.05) were observed in concentrations of ARGs (except tetW) and ARB between the advanced biosolid treatment methods (i.e., anaerobic digestion and lime stabilization) and the conventional dewatering and gravity thickening methods.     

Validation of mega composite sampling and nationwide mass inventories for 26 previously unmonitored contaminants in archived biosolids from the U.S National Biosolids Repository

In the present study, archived U.S biosolids from the 2001 Environmental Protection Agency (EPA) National Sewage Sludge Survey were analyzed with an expanded U.S EPA Method 1694, to determine the occurrence of 26 previously unmonitored pharmaceuticals and personal care products (PPCPs) among a total of 120 analytes. The study further served to examine the reproducibility of a mega-composite approach for creating chemical mass inventories in biosolids based on pooled samples from wastewater treatment plants (WWTPs) nationwide. Five mega-composites reflecting 94 WWTPs in 32 states and the District of Columbia were constructed from archived biosolids and analyzed by LC/ESI-MS/MS using a newly introduced analytical method expanding upon U.S EPA Method 1694. In addition, soil-biosolids mixtures from a mesocosm setup were analyzed to experimentally determine the half-lives of biosolids-borne compounds applied on U.S land. Among 59 analytes detected, 33 had been reported previously, whereas 26 are reported in biosolids for the first time, at levels ranging from 1.65 to 673 μg kg⁻¹ dry weight. Newly recognized biosolids constituents were identified as Ca²⁺ channel blockers, antidepressants, diuretics, β-blockers and analgesics. Using a mass balance approach, the total loading of these 26 pharmaceuticals to U.S soils from biosolids land application was estimated at 5-15 tons year⁻¹. Past and present datasets for 30 pharmaceuticals and personal care products (PPCPs) were determined to be statistically indistinguishable (paired t-test; p = 0.01). This study expands the list of PPCPs reported in U.S biosolids, provides the first estimates of nationwide release rates to and environmental half-lives in U.S agricultural soils, and confirms the utility of using mega-composite sampling for economical tracking of chemical inventories in biosolids on a national scale.     

水曲柳林下凋落物热解特性及动力学分析

利用热重分析法对水曲柳林下凋落物的热解行为进行研究,分析不同的试验气氛、升温速率及粒径对热解过程的影响,采用Coast-Redfern 法进行动力学分析。结果表明：林下凋落物热解分为失水、轻微失重、主要失重和炭化4 个阶段,试样的稳定性大小依次为：水曲柳树枝>水曲柳树皮>水曲柳树叶>福王草;试样在氮气气氛下有1 个失重峰,在空气气氛下有2 个失重峰,在空气气氛下失重率较大,热解更充分;随着升温速率增加,热失重曲线向高温侧移动,失重速率增加,且存在滞后效应;粒径大小对试验影响较小,60 目粒径试样失重率最大;4 种试样活化能由大到小分别为水曲柳树枝、水曲柳树皮、水曲柳树叶和福王草。     

Laccase-catalyzed conversion of natural and synthetic hormones from a municipal wastewater

The Trametes versicolor-derived laccase-catalyzed oxidation of natural estrogens (estrone--E1; 17beta-estradiol--E2; and estriol--E3) and a synthetic estrogen (17alpha-ethinylestradiol--EE2) was studied in synthetic water and municipal wastewater to optimize the process for steroid estrogen removal in wastewater. The optimal pH for each studied steroid estrogen oxidation was approximately 6 in synthetic water. This research also focused on the wastewater matrix effect on developed enzymatic treatment. At pH 7.0 and 25+/-1 degrees C, the experiments showed that the laccase-catalyzed system for the removal of steroid estrogens was not significantly affected by the municipal wastewater matrix. Laccase activity of 20 U/ml was sufficient to achieve complete removal of studied steroid estrogens in both synthetic water and municipal wastewater. Moreover, 1-hydroxy-benzotriazole, when used as a mediator, improved laccase-catalyzed system efficiency, thus decreasing the overall cost of the enzymatic system.     

Behavior of pharmaceuticals, cosmetics and hormones in a sewage treatment plant

Two cosmetic ingredients (galaxolide, tonalide), eight pharmaceuticals (carbamazepine, diazepam, diclofenac, ibuprofen, naproxen, roxithromycin, sulfamethoxazole and iopromide) and three hormones (estrone, 17beta-estradiol and 17alpha-ethinylestradiol) have been surveyed along the different units of a municipal Sewage Treatment Plant (STP) in Galicia, NW Spain. Among all the substances considered, significant concentrations in the influent were only found for the two musks (galaxolide and tonalide), two anti-inflammatories (ibuprofen and naproxen), two natural estrogens (estrone, 17beta-estradiol), one antibiotic (sulfamethoxazole) and the X-ray contrast medium (iopromide), where the other compounds studied were below the limit of quantification. In the primary treatment, only the fragrances (30-50%) and 17beta-estradiol (20%) were partially removed. On the other hand, the aerobic treatment (activated sludges) caused an important reduction in all compounds detected, between 35% and 75%, with the exception of iopromide, which remained in the aqueous phase. The overall removal efficiencies within the STP ranged between 70-90% for the fragrances, 40-65% for the anti-inflammatories, around 65% for 17beta-estradiol and 60% for sulfamethoxazole. However, the concentration of estrone increased along the treatment due to the partial oxidation of 17beta-estradiol in the aeration tank.     

Polybrominated diphenyl ethers, perfluorinated alkylated substances, and metals in tile drainage and groundwater following applications of municipal biosolids to agricultural fields

Polybrominated diphenyl ethers (PBDEs), perfluorinated alkylated substances (PFAS), and metals were monitored in tile drainage and groundwater following liquid (LMB) and dewatered municipal biosolid (DMB) applications to silty-clay loam agricultural field plots. LMB was applied (93,500 L ha^− 1) in late fall 2005 via surface spreading on un-tilled soil (SS_LMB), and a one-pass aerator-based pre-tillage prior to surface spreading (AerWay SSD) (A). The DMB was applied (8 Mg dw ha^− 1) in early summer 2006 on the same plots by injecting DMB beneath the soil surface (DI), and surface spreading on un-tilled soil (SS_DMB). Key PBDE congeners (BDE-47, -99, -100, -153, -154, -183, -209) comprising 97% of total PBDE in LMB, had maximum tile effluent concentrations ranging from 6 to 320 ng L^− 1 during application-induced tile flow. SS_LMB application-induced tile mass loads for these PBDE congeners were significantly higher than those for control (C) plots (no LMB) (p < 0.05), but not A plots (p > 0.05). PBDE mass loss via tile (0-2 h post-application) as a percent of mass applied was ~ 0.04-0.1% and ~ 0.8-1.7% for A and SS_LMB, respectively. Total PBDE loading to soil via LMB and DMB application was 0.0018 and 0.02 kg total PBDE ha^− 1 yr^− 1, respectively. Total PBDE concentration in soil (0-0.2 m) after both applications was 115 ng g^− 1 dw, (sampled 599 days and 340 days post LMB and DMB applications respectively). Of all the PFAS compounds, only PFOS (max concentration = 17 ng L^− 1) and PFOA (12 ng L^− 1) were found above detectable limits in tile drainage from the application plots. Mass loads of metals in tile for the LMB application-induced tile hydrograph event, and post-application concentrations of metals in groundwater, showed significant (p < 0.05) land application treatment effects (SS_LMB > A > C for tile and SS_LMB and A > C for groundwater for most results). Following DMB application, no significant differences in metal mass loads in tile were found between SS_DMB and DI treatments (PBDE/PFAS were not measured). But for many metals (Cu, Se, Cd, Mo, Hg and Pb) both SS_DMB and DI loads were significantly higher than those from C, but only during < 100 days post DMB application. Clearly, pre-tilling the soil (e.g., A) prior to surface application of LMB will reduce application-based PBDE and metal contamination to tile drainage and shallow groundwater. Directly injecting DMB in soil does not significantly increase metal loading to tile drains relative to SS_DMB, thus, DI should be considered a DMB land application option.     

Thyroid hormones as a potential early biomarker of exposure to 4-nonylphenol in adult male shubunkins (Carassius auratus)

Nonylphenol, an estrogenic-like compound, can induce vitellogenin synthesis in males and immature Teleostean species, but little is known about its effects on thyroid hormones balance. The present study evaluated the potential effects of a single acute exposure to nonylphenol (i.p. injected) on the thyroid and reproductive axis of 250 shubunkins (Carassius auratus). Plasma levels of thyroid hormones were quantified immunoenzymatically by ELISA assay. Nonylphenol induced a significant decrease of thyroxin levels, whereas no effect on triiodothyronine concentrations was detected. No histopathological changes were detected in thyroid or testes. The toxicological data confirmed that nonylphenol exerts an estrogenic effect on male fish. In addition, nonylphenol was suspected to inhibit the thyroid hormones balance, suggesting the thyroid should be included among the other endocrine glands susceptible to endocrine disruption.     

Phytoaccumulation of antimicrobials from biosolids: impacts on environmental fate and relevance to human exposure

Triclocarban and triclosan, two antimicrobials widely used in consumer products, can adversely affect ecosystems and potentially impact human health. The application of biosolids to agricultural fields introduces triclocarban and triclosan to soil and water resources. This research examined the phytoaccumulation of antimicrobials, effects of plant growth on migration of antimicrobials to water resources, and relevance of phytoaccumulation in human exposure to antimicrobials. Pumpkin, zucchini, and switch grass were grown in soil columns to which biosolids were applied. Leachate from soil columns was assessed every other week for triclocarban and triclosan. At the end of the trial, concentrations of triclocarban and triclosan were determined for soil, roots, stems, and leaves. Results indicated that plants can reduce leaching of antimicrobials to water resources. Pumpkin and zucchini growth significantly reduced soil concentrations of triclosan to less than 0.001 mg/kg, while zucchini significantly reduced soil concentrations of triclocarban to 0.04 mg/kg. Pumpkin, zucchini, and switch grass accumulated triclocarban and triclosan in mg per kg (dry) concentrations. Potential human exposure to triclocarban from consumption of pumpkin or zucchini was substantially less than exposure from product use, but was greater than exposure from drinking water consumption. Consequently, research indicated that pumpkin and zucchini may beneficially impact the fate of antimicrobials in agricultural fields, while presenting minimal acute risk to human health.     

Temporal trends of total and potentially available element concentrations in sewage biosolids: a comparison of biosolid surveys conducted 18 years apart

The application of biosolids to agricultural land is becoming increasingly popular because of the many benefits they can offer in terms of improved soil fertility and productivity, and also because land application offers an economically viable disposal option. However, the heavy metal and nutrient content of biosolids are potential causes for concern due to the possibility of their accumulation in soils to levels that may adversely affect the environment. Therefore, total concentrations of elements in biosolids and the fraction potentially available to organisms must be known in order to accurately gauge the risks and to classify the biosolids. In 1983, deVries conducted a survey to determine the total and available contents of elements in biosolids collected from various treatment plants around Australia. We conducted a similar survey on biosolids collected in 2001, and thus were able to identify temporal trends in biosolid characteristics. The 2001 survey included biosolids from several treatment plants sampled in 1983, thus some direct comparisons were possible, and in four cases, it was possible to examine temporal trends in biosolid characteristics within individual treatment plants. Total element concentrations were determined by aqua regia digestion, and available element concentrations were determined by 0.01 M CaCl(2) extraction. Results showed total concentrations of Cu, Mn, Ni, Na, and Ca changed little over the period examined, however the 2001 median values of Cd, Mg, Pb, and Zn were all reduced by 60% or greater. Median total concentration of K was more than 50% higher, and P 120% higher, in the 2001 survey. Changes in the availability of elements surveyed in 1983 and 2001 were varied for different elements and for different biosolids. Extractable element concentrations (viewed as percentages of total concentrations) of Cu, Cd, and Ni all fell by 50-72% between 1983 and 2001, while K extractability fell by 35%.     

Solid phase extraction coupled to liquid chromatography-tandem mass spectrometry analysis of sulfonamides, tetracyclines, analgesics and hormones in surface water and wastewater in Luxembourg

In the early 1990s different studies highlighted the relationship between pharmaceuticals, human health and the environment. Among the emerging contaminants, antibiotics are obviously of high concern, because of their potential for inducing antibiotic resistance. In addition, natural and synthetic hormones are relevant because of their potential endocrine-disrupting effects on wildlife. This investigation focuses on the analysis of four classes of veterinary and human pharmaceuticals (sulfonamides, tetracyclines, analgesics and hormones) in surface water and wastewater in Luxembourg. The selected eleven pharmaceuticals include four sulfonamides (sulfathiazole, sulfamethoxazole, sulfadimethoxine and sulfamethazine), two tetracyclines (tetracycline and oxytetracycline), two analgesics (ibuprofen and diclofenac), and three hormones (2 naturals, estrone and β-estradiol, and a synthetic one, 17-α-ethinyl estradiol). The most innovative parts of this study are the simultaneous extraction of the above-mentioned pharmaceuticals as well as tracking their behaviour during flood events in a small river catchment. The method includes pre-concentration by solid phase extraction using Oasis® HLB (Hydrophilic Lipophilic Balance) which gave superior results compared to Chromabond® C-18EC, Chromabond® EASY and Bond Elut® PLEXA cartridges, also evaluated in this investigation. The analysis of the investigated pharmaceutical compounds is carried out by high performance liquid chromatography coupled to a triple quadrupole mass spectrometer. The limits of quantification were 1 ng L^− 1, except for β-estradiol (2 ng L^− 1) and 17-α-ethinyl estradiol (6 ng L^− 1). Recovery rates range from 70 to 94%, with relative standard deviations between 4 and 19%. Application of this method to river concentration and flood events revealed high concentrations of ibuprofen (10-4000 ng L^− 1), with highest levels during flood events, while concentrations of estrogens (1-240 ng L^− 1) and sulfonamides (1-20 ng L^− 1) were comparatively low.     

Distribution and biokinetic analysis of Pb and Po in poultry due to ingestion of dicalcium phosphate

Dicalcium phosphate (DCP) is used as a calcium supplement for food producing animals (i.e., cattle, poultry and pig). When DCP is produced via wet acid digestion of the phosphate rock and depending on the acid used in the industrial process, the final product can result in enhanced ²¹⁰Pb and ²¹⁰Po specific activities (∼ 2000 Bq·kg⁻¹). Both ²¹⁰Pb and ²¹⁰Po are of great interest because their contribution to the dose received by ingestion is potentially large. The aims of this work are to examine the accumulation of ²¹⁰Pb and ²¹⁰Po in chicken tissues during the first 42 days of life and to build a suitable single-compartment biokinetic model to understand the behavior of both radionuclides within the entire animal using the experimental results. Three commercial corn-soybean-based diets containing different amounts and sources of DCP were fed to broilers during a period of 42 days. The results show that diets containing enhanced concentrations of ²¹⁰Pb and ²¹⁰Po lead to larger specific accumulation in broiler tissues compared to the blank diet. Radionuclides do not accumulate homogeneously within the animal body: ²¹⁰Pb follows the calcium pathways to some extent and accumulates largely in bones, while ²¹⁰Po accumulates to a large extent in liver and kidneys. However, the total amount of radionuclide accumulation in tissues is small compared to the amounts excreted in feces. The single-compartment non-linear biokinetic model proposed here for ²¹⁰Pb and ²¹⁰Po in the whole animal takes into account the size evolution and is self-consistent in that no fitting parameterization of intake and excretions rates is required.     

Occurrence of androgens and progestogens in wastewater treatment plants and receiving river waters: Comparison to estrogens

Research has shown that exposure to androgens and progestogens can cause undesirable biological responses in the environment. To date, however, no detailed or direct study of their presence in wastewater treatment plants has been conducted. In this study, nine androgens, nine progestogens, and five estrogens were analyzed in influent and final effluent wastewaters in seven wastewater treatment plants (WWTPs) of Beijing, China. Over a period of three weeks, the average total hormone concentrations in influent wastewaters were 3562 (Wujiacun WWTP)-5400 ng/L (Fangzhuang WWTP). Androgens contributed 96% of the total hormone concentrations in all WWTP influents, with natural androgen (androsterone: 2977 ± 739 ng/L; epiandrosterone: 640 ± 263 ng/L; and androstenedione: 270 ± 132 ng/L) being the predominant compounds. The concentrations of synthetic progestogens (megestrol acetate: 41 ± 25 ng/L; norethindrone: 6.5 ± 3.3 ng/L; and medroxyprogesterone acetate: 6.0 ± 3.2 ng/L) were comparable to natural ones (progesterone: 66 ± 36 ng/L; 17α,20β-dihydroxy-4-progegnen-3-one: 4.9 ± 1.2 ng/L; 21α-hydroxyprogesterone: 8.5 ± 3.0 ng/L; and 17α-hydroxyprogesterone: 1.5 ± 0.95 ng/L), probably due to the wide and relatively large usage of synthetic progestogens in medical therapy. In WWTP effluents, androgens were still the dominant class accounting for 60% of total hormone concentrations, followed by progestogens (24%), and estrogens (16%). Androstenedione and testosterone were the main androgens detected in all effluents. High removal efficiency (91-100%) was found for androgens and progestogens compared with estrogens (67-80%), with biodegradation the major removal route in WWTPs. Different profiles of progestogens in the receiving rivers and WWTP effluents were observed, which could be explained by the discharge of a mixture of treated and untreated wastewater into the receiving rivers.     

Cytotoxic and genotoxic potential of drinking water: a comparison between two different concentration methods

The level of exposure to hazardous compounds through drinking water is low but it is maintained throughout life, therefore representing a risk factor for human health. The use of techniques averaging the consumer's exposure over time could be more useful than relying on intermittent grab samples that may misrepresent average tap water concentrations due to short-term temporal variability. In this study, we compared the induction of in vitro cytotoxic and genotoxic effects (DNA damage by the comet assay) in relation to different sampling methods, i.e. exposure over time (semipermeable membrane devices, SPMDs, exposed for 30 days) or intermittent grab samples (5 weekly water sampling, C18 concentration). Waters with different chemical characteristics were sampled to test the sensitivity of the two methods. We did not found any positive correlation between the biological findings and water chemical parameters. SPMD extracts induced a significantly greater DNA damage than C18. The different behaviour was specially found for the water samples with a low level of organic compounds and when C18 extracts were highly cytotoxic. Our findings suggest that SPMD could be of a great interest in assessing genotoxic contaminants in both raw and drinking water, with great suitability for continuous monitoring. Furthermore, the results of this study have confirmed the great importance of the biological assays in evaluating the effects of a complex mixture such as water in addition to the conventional chemical examination of water quality.