Evaluation of “Classic” and Emerging Contaminants Resulting from the Application of Biosolids to Agricultural Lands: A Review

The presence of detectable amounts of contaminants in treated sewage sludge (concentrations μg/kg – mg/kg) has led to concerns that land applications of biosolids may result in an accumulation of contaminants in the soil and their subsequent translocation through the food chain. Despite advances in wastewater management (e.g., anaerobic, thermophilic, and mesophilic digestion), many compounds and their metabolites remain intact following treatment. This review looks at the main risk factors relating to the occurrence of “classic” (persistent organic pollutants [POPs]) and emerging pollutants (pharmaceuticals and personal care products) in biosolids. Relevant EU legislation and risk assessment strategies for the control of emerging contaminants are also considered. Organic pollutants regulated under the Stockholm Convention on POPs along with PPCPs were identified as contaminants of concern based on the risk factors: persistence, bioaccumulation, and toxicity (PBT). PPCPs were recognized as being of particular concern as their high transformation/removal rates are compensated by their continuous introduction into the environment. This study highlights the growing concern in relation to emerging contaminants in biosolids and highlights risk assessment strategies that can be used to characterize potential human/environmental risks.     

不同预处理条件对海水养殖废弃物发酵产氢的影响

【目的】利用海水养殖场有机废弃物厌氧发酵产氢,可在减少有机污染物的同时获取氢气。【方法】以海水养殖场有机废弃物为底物,比较嗜热酶(S-TE)、酸、碱、灭菌、微波不同预处理方法对厌氧发酵产氢效果的影响,并对发酵过程中底物性质变化[SCOD、可溶性蛋白质、可溶性糖、pH、VFAs(挥发性脂肪酸)和乙醇]进行探讨。【结果】灭菌预处理产氢效果最好,产氢率为22.0 mL/g VSS,酸处理的效果最差,产氢率为7.6 mL/g VSS。可溶性糖大量消耗之后,氢气不再产生。接种S-TE预处理污泥的底物能更多地释放营养物质,并在整个发酵过程中保持较为稳定的pH值。发酵过程中产生的VFAs主要成分是乙酸,在发酵后期出现乙醇。【结论】灭菌预处理是海水养殖场有机废弃物厌氧发酵产氢的最佳预处理方法,可溶性糖为这一过程主要的营养来源。     

Pectinase production by a Brazilian thermophilic fungus <Emphasis Type="Italic">Thermomucor indicae-seudaticae</Emphasis> N31 in solid-state and submerged fermentation

Thermophilic organisms produce thermostable enzymes, which have a number of applications, justifying the interest in the isolation of new thermophilic strains and study of their enzymes. Thirty-four thermophilic and thermotolerant fungal strains were isolated from soil, organic compost, and an industrial waste pile based on their ability to grow at 45°C and in a liquid medium containing pectin as the only carbon source. Among these fungi, 50% were identified at the genus level as Thermomyces, Aspergillus, Monascus, Chaetomium, Neosartoria, Scopulariopsis, and Thermomucor. All isolated strains produced pectinase during solid-state fermentation (SSF). The highest polygalacturonase (PG) activity was obtained in the culture medium of thermophilic strain N31 identified as Thermomucor indicae-seudaticae. Under SSF conditions on media containing a mixture of wheat bran and orange bagasse (1 : 1) at 70% of initial moisture, this fungus produced the maximum of 120 U/ml of exo-PG, while in submerged fermentation (SmF) it produced 13.6 U/ml. The crude PG from SmF was more thermostable than that from SSF and exhibited higher stability in acidic pH.     

Efficient release of ferulic acid from sweet potato (<Emphasis Type="Italic">Ipomoea batatas</Emphasis>) stems by chemical hydrolysis

An efficient method for release of ferulic acid from sweet potato stems was developed. Ferulic acid along with phenolic compounds were released from stems by acid and alkaline treatments. The base hydrolysis with 0.1 N NaOH yielded the highest quantity of total extracts (471.1 mg/g). The stems released more phenolic compounds when 0.0125∼0.025 N NaOH was employed. Where as ferulic acid release was maximal with 0.05 N H₂SO₄ (0.32 mg/g). Ferulic acid was separated from phenolics by column chromatography. Among the elution solvents, ethyl acetate fractions (80%) contained ferulic acid. Ethyl acetate eluants were further fractionated with n-hexane/ethyl acetate/formic acid (100/50/0.5, v/v/v). All fractions showed ferulic acid and phenolic compounds. Fraction V among them was ascribed to ferulic acid with an yield of 5.41 mg/g of dry sweet potato tissue.     

Sensitivity of thermophilic methanogenic bacteria to heavy metals

The effects of Cd, Cu, and Ni on pure cultures of thermophilic methanogenic bacteria were studied. The bacteria used wereMethanobacterium thermoautotrophicum and TAM, a thermophilic, acetate-decarboxylating, methanogenic bacterium. Much lower concentrations of heavy metals were needed to cause initial inhibition of TAM (1 mg/liter Cu and Cd; 5 mg/liter Ni) compared withM. thermoautotrophicum (10 mg/liter Cu and Cd; and 100 mg/liter Ni). No growth of TAM occurred at 5 mg/liter Cu and 25 mg/liter Ni, while the corresponding values forM. thermoautotrophicum were 50 mg/liter Cu and 200 mg/liter Ni. Cd (50 mg/liter) was totally inhibitory toM. thermoautotrophicum but allowed minimal growth of TAM. Ni stimulated both organisms at an optimal concentration of 5 mg/liter forM. thermoautotrophicum and 1 mg/liter for TAM. The toxicity of Cd and Cu was found to depend upon the presence of Ni in the medium.     

Degradation of waste waters from olive oil mills by Yarrowia lipolytica ATCC 20255 and Pseudomonas putida

Waste waters from olive oil processing may cause severe pollution in the Mediterranean area, since they have a high level of chemical oxygen demand (COD) (100–200 g/l) and contain other organic and inorganic compounds. In all olive oil producing countries, the reduction of pollution in olive oil mill waste waters at reasonable costs and using techniques suitable for most industrial applications is an unsolved problem. For this paper, the yeast Yarrowia lipolytica ATCC 20255 was grown on waste waters from an olive oil mill in a 3.5 1 fermenter under batch culture conditions. The results showed that the yeast was capable of reducing the COD value by 80% in 24 h. In this way, a useful biomass of 22.45 g/l as single cell protein (SCP) and enzyme lipase were produced. During this process, most of the organic and inorganic substances were consumed, only aromatic pollutants were still present in the fermentation effluents. Therefore, we used a phenol degrader, namely Pseudomonas putida, to reduce phenolic compounds in the fermentation effuents after removing Yarrowia lipolytica cells. P. putida was effective in reducing phenols in only 12 h.     

Background levels of polycyclic aromatic hydrocarbons (PAH) and selected metals in new England urban soils

Polycyclic aromatic hydrocarbons (PAH) are byproducts of combustion and are ubiquitous in the urban environment They are also present in industrial chemical wastes, such as coal tar, petroleum refinery sludges, waste oils and fuels, and wood‐treating residues. Thus, PAHs are chemicals of concern at many waste sites. Risk assessment methods will yield risk‐based cleanup levels for PAHs that range from 0.1 to 0.7 mg/kg. Given their universal presence in the urban environment, it is important to compare risk‐based cleanup levels with typical urban background levels before utilizing unrealistically low cleanup targets. However, little data exist on PAH levels in urban, nonindustrial soils. In this study, 60 samples of surficial soils from urban locations in three New England cities were analyzed for PAH compounds. In addition, all samples were analyzed for total petroleum hydrocarbons (TPH) and seven metals. The upper 95% confidence interval on the mean was 3 mg/kg for benzo(a)pyrene toxic equivalents, 12 mg/kg for total potentially carcinogenic PAH, and 25 mg/kg for total PAH. The upper 95% confidence interval was 373 mg/kg for TPH, which exceeds the target level of 100 mg/kg used by many state regulatory agencies. Metal concentrations were similar to published background levels for all metals except lead. The upper 95% confidence interval for lead was 737 mg/kg in Boston, 463 mg/kg in Providence, and 378 mg/kg in Springfield.     

Microbial oxidation of dibenzothiophene by the thermophilic organism Sulfolobus acidocaldarius

The refractory organic sulfur compound dibenzothiophene (DBT) has been oxidized by the thermophilic, sulfur oxidizing organism Sulfolobus acidocaldarius. Sulfate ions were released into the medium as the oxidation product. The kinetics of this oxidation have been investigated on the basis of sulfate released as a result of oxidation. Dibenzothiophene was found to be inhibitory to the organisms for initial concentrations over 500 mg/L. The organism may prove to be capable of oxidizing thiophene compounds present in oil refinery wastewater, coal, and crude oil.     

Organic matter release by dominant hermatypic corals of the Northern Red Sea

Particulate organic matter (POM) and dissolved organic carbon (DOC) release by six dominant hermatypic coral genera (Acropora, Fungia, Goniastrea, Millepora, Pocillopora and Stylophora) were measured under undisturbed conditions by laboratory incubations during four seasonal expeditions to the Northern Red Sea. In addition, the influence of environmental factors (water temperature, light availability and ambient inorganic nutrient concentrations) was evaluated. Particulate organic carbon (POC) and particulate nitrogen (PN) release were always detectable and genus-specific, with Stylophora releasing most POM (6.5 mg POC and 0.5 mg PN m⁻² coral surface area h⁻¹) during all seasons. The fire coral Millepora released significantly less POM (0.3 mg POC and 0.04 mg PN m⁻² coral surface area h⁻¹) than all investigated anthozoan genera. The average POC:PN ratio of POM released by all coral genera was 12 ± 1, indicating high carbon/low nitrogen content of coral-derived organic matter. POM release showed little seasonal variation, but average values of POC and PN release rates correlated with water temperature, light availability and ambient nitrate concentrations. DOC net release and elevated DOC:POC ratios were detectable for Acropora, Goniastrea and Millepora, revealing maximum values for Acropora (30.7 mg DOC m⁻² coral surface area h⁻¹), whilst predominant DOC uptake was observed for Pocillopora, Fungia and Stylophora. Depth-mediated light availability influenced DOC fluxes of Acropora and Fungia, while fluctuations in water temperature and ambient inorganic nutrient concentrations showed no correlation. These comprehensive data provide an important basis for the understanding of coral reef organic matter dynamics and relevant environmental factors.     

Low‐temperature (9°C) AMD treatment in a sulfidogenic bioreactor dominated by a mesophilic Desulfomicrobium species

The possibilities for the treatment of low‐temperature mine waste waters have not been widely studied. The amenability of low‐temperature sulfate reduction for mine waste water treatment at 9°C was studied in a bench‐scale fluidized‐bed bioreactor (FBR). Formate was used as the electron and carbon source. The first influent for the FBR was acidic, synthetic waste water containing iron, nutrients, and sulfate, followed by diluted barren bioleaching solution (DBBS). The average sulfate reduction rates were 8 mmol L^?1 day^?1 and 6 mmol L^?1 day^?1 with synthetic waste water and DBBS, respectively. The corresponding specific activities were 2.4 and 1.6 mmol SO g VSS^?1 day^?1, respectively. The composition of the microbial community and the active species of the FBR was analyzed by extracting the DNA and RNA, followed by PCR‐DGGE with the universal bacterial 16S rRNA gene primers and dsrB‐primers specific for sulfate‐reducing bacteria. The FBR microbial community was simple and stable and the dominant and active species belonged to the genus Desulfomicrobium. In summary, long‐term operation of a low‐temperature bioreactor resulted in enrichment of formate‐utilizing, psychrotolerant mesophilic sulfate reducing bacteria. Biotechnol. Bioeng. 2009; 104: 740–751 © 2009 Wiley Periodicals, Inc.     

山东省部分水岸带土壤重金属含量及污染评价

为了解山东省水岸带土壤重金属的含量特征和污染状况,于2010年9月—10月采集了39个水岸带土壤样品,分析了土壤中Cr、Co、Ni、Cu、Zn、Cd、Pb和Hg的含量以及土壤的pH值、粒度和有机质,采用单因子指数法、综合指数法和潜在生态危害指数法对水岸带土壤重金属污染进行了评价,并利用相关分析和聚类分析对其来源进行了初步的解析。结果表明：水岸带土壤的pH值为5.67—8.66,主要呈碱性;有机质的平均含量为9.39 g/kg,土壤粒度主要以砂粒和粉粒为主,其平均体积百分比分别为50.33%和38.48%,平均粒径为89.69 μm;Cr、Co、Ni、Cu、Zn、Cd、Pb和Hg的平均含量为53.03 mg/kg、10.33 mg/kg、24.96 mg/kg、18.38 mg/kg、56.13 mg/kg、0.142 mg/kg、22.48 mg/kg和0.020 mg/kg。各水岸带土壤重金属的含量均符合《土壤环境质量标准》（GB15618-1995）二级标准。以山东省土壤元素背景值为评价标准,水岸带土壤重金属总体表现为轻度污染和轻微生态风险,其中Cd和Hg是主要的污染因子,其对潜在生态危害指数的平均贡献率分别为46.8% 和33.6%。洙赵新河、廖河、门楼水库和东平湖水岸带土壤重金属污染及潜在生态危害明显高于其他水源地。源解析的结果表明：水岸带土壤重金属的含量受自然源和人为源的双重影响,人为源主要包括地表径流、工业废气、垃圾和交通运输等。     

Comparative absorption and tissue distribution of <Superscript>14</Superscript>C-benzo(a)pyrene and <Superscript>14</Superscript>C-phenanthrene in the polar cod (<Emphasis Type="Italic">Boreogadus saida</Emphasis>) following oral administration

The Arctic is an important sink for organic pollutants such as polycyclic aromatic hydrocarbons (PAHs) long-range transported from industrial regions. With the retreat of sea ice and increasing anthropogenic activities such as the oil and gas industries, local sources of PAHs are expected to increase both through operational and accidental discharges. There is a need to increase our knowledge concerning the uptake and distribution of organic pollutants, in particular PAHs, to evaluate the risk these toxic compounds may represent for Arctic species. The absorption and tissue distribution of ¹⁴C-benzo(a)pyrene (BaP) and ¹⁴C-phenanthrene (Phen) were studied in the polar cod (Boreogadus saida), a key Arctic species. After a single oral dose of BaP (1.15 ± 0.36 mg/kg fish) or Phen (0.40 ± 0.12 mg/kg fish), corresponding to 0.12 ± 0.03 mCi/kg fish, the tissue distribution was followed through 30 days by means of whole-body autoradiography and liquid scintillation counting of liver and bile. For both compounds, radiolabeling was mainly present in the bile and the intestines throughout the study period. Phen-derived radioactivity, however, appeared to be more systemically distributed compared to BaP. Furthermore, a far higher amount of irreversibly bound BaP-derived radioactivity was present in the intestinal mucosa compared to Phen, indicating a more extensive formation of reactive intermediates from the former compared with the latter. Liquid scintillation counting confirmed that radioactivity was present in the liver at all time points for both groups although the levels were low in the BaP group. These results strongly indicated that both compounds and/or their metabolites undergo enterohepatic circulation.     

Evaluation of HCH,DDT and Endosulfan Levels in Soil by Gas Chromatography/Tandem Mass Spectrometry

Persistent organic pollutants (Σ DDX, Σ HCH, and Σ Endosulfan) were quantified in top soil and deep soil of a pesticide manufacturing industry. It was also possible to identify the presence of some other organochlorinated compounds (OCs) in the soil. A suitable multiresidue analysis of persistent organic pollutants in soil samples was developed based on soxhlet extraction and gas chromatography–mass spectrometry for quantifying parent compounds and degradation products, namely OCs and other miscellaneous pesticides. The quantification protocol was developed using Programmed Temperature Vaporization (PTV) and GC/MS/MS as identification tools. Extraction, PTV and MS/MS conditions were optimized for 11 pesticides with unambiguous spectral confirmation. The protocol has been applied to a large number of environmental samples and has proved to be reliable. The degradation ratios between the parent substances and their metabolites (DDX and HCH isomers) were calculated to determine whether there were any fresh inputs of parent pesticide at the site. Pesticide concentrations in the low to high concentration range (159 μ g/kg to 133 mg/kg) have been measured. The investigations clearly indicate pesticide contamination in the soil.     

Health risks associated with municipal waste combustion on the example of Laskowa commune (Southern Poland)

This study presents the results of an analysis of combustion waste, namely fly ashes produced from the burning of solid fuels mixed with municipal waste. Heavy metal concentrations in the fly ashes examined fell within the following ranges (mg/kg): Cd 0.39–0.79, Cr 13.48–58.51, Ni 17.01–49.37 and Pb 14.95–59.74. As this type of waste does not exceed the limit values of pollutants for organic and organic-mineral fertilisers, it is often discarded on agricultural land or dumped in illegal landfills. Fine particles of fly ashes travel considerable distances and pose a risk to human health as they stick to people's hands during field works. The mean hazard quotient (HQ) values for non-carcinogenic forms of the elements analysed were 1.06E+00 for children and 1.47E-01 for adults. A HQ>1 indicates the probability of adverse health effects. The study has shown that the dominant exposure pathway was ingestion, which accounted for approx. 91% of total health risk, while the respective percentages for other pathways were less than 9% for dermal contact and 0.05% for inhalation. The highest health risk in the ingestion exposure pathway was observed for Cr (HQ_ing = 4.50E-01 for children, HQ_ing = 5.23E-02 for adults) and Pb (HQ_ing = 4.31E-01 for children, HQ_ing = 5.01E-02 for adults). Health risk associated with the presence of Ni and Cd in the material analysed was markedly lower. For carcinogenic forms, the Risk index was established at 6.13E-08 for children and 2.13E-07 for adults. As the exposure limit (10E-5) was not exceeded, the conditions in the area studied should be considered satisfactory.     

Pollution of the Amur River with anthropogenic and natural organic substances

The pollution of the Amur water with organic compounds at the Khabarovsk water-supply point has been analyzed by means of gas chromatography-mass spectrometry (GC-MS). Among environmental pollutants, petroleum hydrocarbons and alkylphtalates predominate. A number of potentially dangerous compounds present in the waste water of the rubber industry works and some other dangerous compounds including a herbicide of TsP 32179 type were detected. Pollution with these compounds has a stable character. The concentrations of a number of critical substances did not exceed the MPCs; however, many compounds are toxic micro-impurities. A great part of the identified compounds are of microbiological origin.     

Fundamental analysis of real-time PCR quantification and modeling for thermophilic <Emphasis Type="SmallCaps">L</Emphasis>-lactate fermentation by <Emphasis Type="Italic">Bacillus coagulans</Emphasis> from glucose

Batch and semi-continuous thermophilic l-lactate fermentation experiments were performed using Bacillus coagulans and glucose as a substrate. Reactor performance and biomass concentrations were assessed using two methods: turbidity as a traditional biomass index and real-time polymerase chain reaction (PCR) quantification of 16S rRNA genes. In the batch experiment, although the relationship between turbidity and real-time PCR assay differed depending on the growth phase, a correlation was observed between both assay methods. In the semi-continuous experiment, real-time PCR measurement was well suited for use as an index for evaluating bacterial mass under different organic loading conditions. A mathematical model was applied to evaluate the real-time PCR quantification to long-term, semi-continuous lactate fermentation. Lactate fermentation was well suited since only B. coagulans was involved in the reactions. The results obtained revealed a fundamental relationship between real-time PCR and traditional biomass analyses.     

Cloning of <Emphasis Type="SmallCaps">l</Emphasis>-lactate dehydrogenase and elimination of lactic acid production via gene knockout in<Emphasis Type="Italic"> Thermoanaerobacterium saccharolyticum</Emphasis> JW/SL-YS485

The gene encoding l-lactate dehydrogenase from Thermoanaerobacterium saccharolyticum JW/SL-YS485 was cloned, sequenced, and used to obtain an l-ldh deletion mutant strain (TD1) following a site-specific double-crossover event as confirmed by PCR and Southern blot. Growth rates and final cell densities were similar for strain TD1 and the wild-type grown on glucose and xylose. Lactic acid was below the limit of detection (0.3 mM) for strain TD1 on both glucose and xylose at all times tested, but was readily detected for the wild-type strain, with average final concentrations of 8.1and 1.8 mM on glucose and xylose, respectively. Elimination of lactic acid as a fermentation product was accompanied by a proportional increase in the yields of acetic acid and ethanol. The results reported here represent a step toward using metabolic engineering to develop strains of thermophilic anaerobic bacteria that do not produce organic acids, and support the methodological feasibility of this goal.     

Removal of Pb2+ and Ni2+ by bio-sludge in sequencing batch reactor (SBR) and granular activated carbon-SBR (GAC-SBR) systems

Living bio-sludge from domestic wastewater treatment plant was used as adsorbent of heavy metals (Pb(2+), Ni(2+)) and its adsorption capacity was about 10-30% reduced by autoclaving at 110 degrees C for 10 min. The living bio-sludge acclimatized in synthetic industrial estate wastewater (SIEWW) without heavy metals showed the highest Pb(2+) and Ni(2+) adsorption capacities at 840+/-20 and 720+/-10 mg/g bio-sludge, respectively. The adsorbed Pb(2+) and Ni(2+) were easily eluted (70-77%) from bio-sludge by washing with 0.1 mol/l HNO(3) solution. The heavy metals (Pb(2+), Ni(2+)) removal efficiency of both SBR and GAC-SBR systems were increased with the increase of hydraulic retention time (HRT), or the decrease of organic loading. The SBR system showed higher heavy metals removal efficiency than GAC-SBR system at the same organic loading or HRT. The Pb(2+), Ni(2+), BOD(5), COD and TKN removal efficiencies of GAC-SBR system were 88.6+/-0.9%, 94.6+/-0.1%, 91.3+/-1.0%, 81.9+/-1.0% and 62.9+/-0.5%, respectively with industrial estate wastewater (IEWW) with 410 mg/l glucose, 5 mg/l Pb(2+) and 5 mg/l Ni(2+) under organic loading of 1.25 kg BOD(5)/m(3) d (HRT of 3 days). The bio-sludge quality (sludge volume index: SVI) of the system was less than 80 ml/g. The excess sludge from both SBR and GAC-SBR systems with SIEWW under the organic loading of 1.25-2.50 kg BOD(5)/m(3) d contained Pb(2+) and Ni(2+) at concentrations of 240-250 mg Pb(2+)/g bio-sludge and 180-210 mg Ni(2+)/g bio-sludge, respectively.     

Migration of phthalates from plastic products to model solutions

The aim of this investigation was to determine the level and rate of migration of phthalates, compounds used as plastic softeners, from various plastic products into model solutions and to assess the possible adverse effects of the phthalate amounts released on human health, thus to contribute to harmonization of the opinions on the maximal allowed human exposure to these compounds through environmental factors. Nine specimens of plastic toys, 16 specimens of plastic food containers and 10 specimens of other plastic consumer goods were analyzed. The specimens of plastic products were submitted to 10-day action of model solutions. Three model solutions were used: distilled water, 10% ethyl alcohol, and 3% acetic acid. Identification and quantification of the phthalates released were performed by the method of gas chromatography on days 1, 5 and 10 of exposure, at a detection limit of 0.005 microgram/kg. On day 10, the highest level of released phthalates (54.5 mg/kg) was measured in distilled water, followed by 44.4 mg/kg in 3% acetic acid and 32.3 mg/kg in 10% ethyl alcohol. According to plastic product categories, the highest pooled level of phthalates released to all three solutions was recorded for plastic toys (66.2 mg/kg), followed by food containers (37.6 mg/kg) and other consumer goods (27.4 mg/kg). According to plastic product categories, toys showed the most rapid phthalate release, with 65.4% (43.3 of 66.2 mg/kg) of the pooled level of phthalates released to all three solutions recorded on day 1. As indicated by the study results, the levels of phthalates released would not present a hazard for human health, not even over a prolonged period of time. However, data on the highest and fastest pooled phthalate release from plastic toys, and this especially to distilled water simulating salivary action, point to the need of continuous evaluation and amendments of the legislation on phthalates in consumer goods.     

有机酸对菜地土壤磷素活化的影响

实验室模拟研究两种有机酸(柠檬酸、草酸)对菜地土壤磷素活化的影响。结果表明:有机酸对菜地土壤磷的活化效果较明显,且随有机酸浓度的增加,土壤磷活化效果越显著。两种有机酸的活化效果为草酸>柠檬酸。有机酸对磷的活化效果与土壤Olsen- P含量、有机质含量呈显著正相关关系。土壤中有效磷的释放随着有机酸浸提时间的延长而逐渐增加。