Cycling of volatile organic sulfur compounds in anaerobically digested biosolids and its implications for odors.

The objectives of this research were to elucidate the mechanisms for production and degradation of volatile organic sulfur compounds (VOSCs), key odor causing compounds produced by biosolids. These compounds included methanethiol (MT), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS). A series of experiments were used to probe various pathways hypothesized to produce and degrade these VOSCs. The production of MT was found to mainly occur from degradation of methionine and the methylation of hydrogen sulfide. DMS was formed through the methylation of MT. DMDS was formed by MT oxidation. All three of the VOSCs were readily degraded by methanogens and a cyclic pathway was proposed to describe the production and degradation of VOSCs. The research demonstrated that the main source of VOSCs was the biodegradation of protein within the biosolids and the results provided a framework for understanding the production of odor from anaerobically digested sludges before and after dewatering.     

Generation pattern of sulfur containing gases from anaerobically digested sludge cakes.

Eleven dewatered sludge cakes collected from anaerobic digesters at different treatment plants were evaluated for the amount, type, and pattern of odorous gas production. All but one of the sludge cakes were from mesophilic anaerobic digesters. One was from a thermophilic digester. The pattern and quantities of sulfur gases were found to be unique for each of the samples with regard to the products produced, magnitude, and subsequent decline. The main odor-causing chemicals were volatile sulfur compounds, which included hydrogen sulfide, methanethiol, and dimethyl sulfide. Volatile sulfur compound production peaked in 3 to 8 days and then declined. The decline was a result of conversion of organic sulfur compounds to sulfide. In one side-by-side test, a high-solids centrifuge cake generated more odorous compounds than the low-solids centrifuge cake. The data show that anaerobic digestion does not eliminate the odor potential of anaerobically digested dewatered cakes.     

Measurement of biosolids compost odor emissions from a windrow, static pile, and biofilter.

A pilot study was conducted to compare odor emissions from a windrow process and an aerated static pile and to determine the odor reduction efficiency of a pilot two-phase biofilter for odor control of biosolids composting. Chemical compounds identified as responsible for odors from biosolids composting include ammonia, dimethyl disulfide, carbon disulfide, formic acid, acetic acid, and sulfur dioxide (or carbonyl sulfide). Aeration was found to reduce the concentration of ammonia, formic acid, and acetic acid by 72, 57, and 11%, respectively, compared with a nearby windrow, while dimethyl sulfide, carbon disulfide, and sulfur dioxide (or carbonyl sulfide) concentrations were below detection limits. Using dilution-to-threshold olfactometry, aeration followed by biofiltration was found to reduce the odor from biosolids composting by 98%. Biofiltration also altered the character of odor emissions from biosolids composting, producing a less offensive odor with an earthy character. Biofiltration was found to reduce the concentration of ammonia, dimethyl disulfide, carbon disulfide, formic acid, acetic acid, and sulfur dioxide (or carbonyl sulfide) by 99, 90, 32, 100, 34, and 100%, respectively. The concentrations of those odorants were estimated to be 3700, 110000, 26,37,5, and 1.2 times reported human detection limits before the two-phase biofilter, respectively, and 42,9600,18,0,3, and 0 times human detection limits after the biofilter, respectively.     

Bioleaching of zinc and copper from anaerobically digested swine manure: effect of sulfur levels and solids contents.

Anaerobically digested swine manure (ADSM) generally contains high concentrations of zinc (Zn) and copper (Cu). These metals levels exceed the land application regulations of municipal biosolids of many European countries and are on the borderline of exceptional quality in the U.S. Environmental Protection Agency (U.S. EPA) 40 CFR part 503 standards. From this perspective, a series of batch tests were conducted to evaluate the feasibility of bioleaching of Zn and Cu from ADSM so that the produced biosolids could safely be applied to land. The effect of different substrate levels (sulfur) and total solids content (as high as 9%) on metal solubilization was investigated. The results showed that metal solubilization efficiency for both Zn and Cu declined significantly with an increase in total solids from 3 to 6% and then to 9% at the same substrate level. Metal solubilization increased proportionately with increases in substrate concentration up to 6% of total solids content. However, at 9% total solids content, metal solubilization was insignificant at all substrate levels tested. At a 6% total solids level and 10 000 mg/L of substrate, 94% of Zn and 72% of Cu were solubilized. Bioleaching was also found to be effective in destruction of pathogens with approximately 2.5 log-scale reduction. The residual biosolid was found to meet the Class A biosolids standands of U.S. EPA 40 CFR part 503.     

Pyrolysis of humic acids from digested and composted sewage sludge

Humic acids (HAs) were extracted from four digested sewage sludge samples composted for four months, one, two and four years. HAs were pyrolyzed at three different temperatures applying both conventional and in situ methylation (ISM) pyrolysis. The pyrolysates were analyzed using gas chromatography-mass spectrometry (GC/MS). Derivatization (ISM) and pyrolysis temperature had dramatic effects on the composition and relative amounts of the pyrolysates. Among the derivatized HA fragments aliphatic compounds prevailed under all the pyrolysis conditions tested. Aromatic substances consisting mainly of guaiacyl-type compounds were detected in higher abundances only at elevated temperatures. Without ISM the contribution of aromatic structures to the total pyrogram was considerably greater than that of the aliphatics. Increase of the pyrolysis temperature from 450 degrees C to 600 degrees C had smaller effect on the proportions and composition of the compounds studied than increase from 350 degrees C to 450 degrees C.     

A comparative study of anaerobically digested and undigested sewage sludges in preparation of activated carbons.

Disposal of sewage sludge is an increasingly expensive and environmentally sensitive problem throughout the world. Preparation of activated carbon from sewage sludge offers an attractive re-use alternative to the traditional disposal routes. The objective of this research work was to compare anaerobically digested sewage sludge (DS) and undigested sewage sludge (US) as source materials in the preparation of activated carbons. Prior to the preparation the properties of the two types of sewage sludges were determined and compared. Subsequently the sludge samples were activated with 5 M ZnCl2 solution and thereafter pyrolysed at heating temperature of 650 degrees C for 2 h with the heating rate of 15 degrees C/min under a nitrogen atmosphere. The produced activated carbons were characterised by surface area and porosity analysis, CHN elemental composition and ash contents determination, and aqueous phase phenol adsorption tests. The results indicate that in comparison with the DS, the US had a higher carbon content and lower ash content, and accordingly yielded a better activated carbon with a higher BET surface area, pore volume, carbon content and phenol adsorption capacity.     

The effects of pH, bromide and nitrite on halonitromethane and trihalomethane formation from amino acids and amino sugars

In this study, the effects of pH, bromide and nitrite on the formation of halonitromethanes (HNMs) and trihalomethanes (THMs) from eight amino acids (glycine, alanine, serine, cysteine, aspartic acid, glutamic acid, lysine and histidine) and four amino sugars (glucosamine, galactosamine, N-acetylglucosamine and N-acetylneuraminic acid) were examined for chlorination and ozonation followed by chlorination. During ozonation-chlorination, two amino acids, glycine and lysine, exhibited distinctly higher HNM formation than the other compounds. The formation of HNMs was higher at pH 8 than 6. Glycine and lysine also produced higher levels of THMs than the other compounds at pH 8. The presence of nitrite resulted in an increase in HNM formation. The presence of bromide increased the HNM formation, especially brominated HNM species. Bromine incorporation factors of trihalogenated HNMs were higher than those of THMs. For chlorination alone, HNM levels were about the detection limit (4 nM or 0.7 μg L⁻¹) at pH 6 and 8, and in the presence of bromide or nitrite. Amino acids and amino sugars tested, except glycine and lysine, showed relatively low levels of THM (∼15 μg L⁻¹) formation.     

Impact of drying and composting procedures on the concentrations of 4-nonylphenols, di-(2-ethylhexyl)phthalate and polychlorinated biphenyls in anaerobically digested sewage sludge

Enhanced treatments of sewage sludge produce a more manageable product for agricultural use by stabilizing the material, removing water, and reducing the possibility of pathogen transfer. We investigated the impact of pilot-scale composting and drying of sludge on physicochemical characteristics and on the concentrations of some organic contaminants. During the 143 day composting procedure, organic matter fell 22% and moisture by half. Concentrations of 4-nonylphenols (4-NPs) fell by 88% and di-(2-ethylhexyl) phthalate (DEHP) by 60%; losses continued throughout the procedure. Losses of total polychlorinated biphenyls (PCBs) were 11%, mostly from the lower molecular weight congeners, suggesting volatilization as the most likely loss mechanism. The drying process was much shorter, 40 days, yet organic matter content decreased by 27% and moisture by 85%. Losses of 4-NPs (39%) and DEHP (22%) were less than in composting and stopped when moisture content became constant. There were no losses of PCBs. Both treatments are simple, practical procedures that reduce the volume of waste and are applicable in situ on farms. Composting would be the method of choice for reducing organic contaminants but requires much longer times than drying.     

Cytotoxic activity of selenosulfate versus selenite in tumor cells depends on cell line and presence of amino acids

Based on acute cytotoxicity studies, selenosulfate (SeSO₃ ^?) has been suggested to possess a generally higher toxic activity in tumor cells than selenite. The reason for this difference in cytotoxic activity remained unclear. In the present study, cytotoxicity tests with human hepatoma (HepG2), malignant melanoma (A375), and urinary bladder carcinoma cells (T24) showed that the selenosulfate toxicity was very similar between all three tested cell lines (IC₅₀ 6.6–7.1 μM after 24 h). It was largely independent of exposure time and presence or absence of amino acids. What changed, however, was the toxicity of selenite, which was lower than that of selenosulfate only for HepG2 cells (IC₅₀?>?15 μM), but similar to and higher than that of selenosulfate for A375 (IC₅₀ 4.7 μM) and T24 cells (IC₅₀ 3.5 μM), respectively. Addition of amino acids to T24 cell growth medium downregulated short-term selenite uptake (1.5 versus 12.9 ng Se/10⁶ cells) and decreased its cytotoxicity (IC₅₀ 8.4 μM), rendering it less toxic than selenosulfate. The suggested mechanism is a stronger expression of the x_c ^? transport system in the more sensitive T24 compared to HepG2 cells which creates a reductive extracellular microenvironment and facilitates selenite uptake by reduction. Selenosulfate is already reduced and so less affected. The cytotoxic activity of selenosulfate and selenite to tumor cells therefore depends on the sensitivity of each cell line, supplements like amino acids as well as the reductive state of the extracellular environment.     

Optimising the preparation of activated carbon from digested sewage sludge and coconut husk.

Preparation of activated carbon from sewage sludge is a promising way to dispose of sewage sludge as well as to produce a low-cost adsorbent for pollutant removal. This research work aimed to optimise the condition for activated carbon preparation from anaerobically digested sewage sludge with the additive coconut husk. The sewage sludge sample was mixed with the additive coconut husk. The preparation condition variables investigated involved the concentration of the ZnCl2 solutions, heating temperature, dwell time and heating rate in pyrolysis and the mixing ratio of coconut husk to sewage sludge. Surface area, pore size distribution, aqueous phenol adsorption capacity and the production yield of the final products were determined and compared. Experimental results revealed that low concentrations of ZnCl2 solution tended to improve the microporosity of the final product. Heating temperature had a considerable impact on the surface area, pore size distribution and phenol adsorption capacity of the final products, whereas dwell time and heating rate performed comparatively insignificantly. The effect of increasing the mixing ratio of coconut husk to sewage sludge was principally to increase the microporosity of the final products. The activated carbon with the highest BET surface area was produced with the activation of 5 M ZnCl2 solution and, thereafter, pyrolysis at a heating temperature of 500 degrees C for 2 h with a heating rate of 10 degrees C/min. The mixing ratio of 1:4 in terms of coconut husk to sewage sludge based on their dried weights was found to be most cost effective.     

Annual variations of odor concentrations and emissions from swine gestation, farrowing, and nursery buildings

To obtain annual odor emission profiles from intensive swine operations, odor concentrations and emission rates were measured monthly from swine nursery, farrowing, and gestation rooms for a year. Large annual variations in odor concentrations and emissions were found in all the rooms and the impact of the seasonal factor (month) was significant (P < 0.05). Odor concentration was low in summer when ventilation rate was high but high in winter when ventilation rate was low, ranging from 362 (farrowing room in July) to 8934 (nursery room in December) olfactory unit (OU) m(-3). This indicates that the air quality regarding odor was significantly better in summer than that in winter. Odor emission rate did not show obvious seasonal pattern as odor concentration did, ranging from 2 (gestation room in November) to 90 (nursery room in April) OU m(-2) sec(-1); this explains why the odor complaints for swine barns have occurred all year round. The annual geometric mean odor concentration and emission rate of the nursery room was significantly higher than the other rooms (P < 0.05). In order to obtain the representative annual emission rate, measurements have to be taken at least monthly, and then the geometric mean of the monthly values will represent the annual emission rate. Incorporating odor control technologies in the nursery area will be the most efficient in reducing odor emission from the farm considering its emission rate was 2 to 3 times of the other areas. The swine grower-finisher area was the major odor source contributing 53% of odor emission of the farm and should also be targeted for odor control. Relatively positive correlations between odor concentration and both H2S and CO2 concentrations (R(2) = 0.58) means that high level of these two gases might likely indicate high odor concentration in swine barns.     

Biosolids-amended soils: Part I. Effect of biosolids application on soil quality and ecotoxicity.

Investigations of potential risk from biosolids generally indicate that land application does not threaten human or ecosystem health, but questions continue to arise concerning the environmental effects of this practice. This research project was initiated to evaluate ecotoxicity resulting from the amendment of soils with biosolids from municipal wastewater treatment plants. Toxicity was evaluated using standard tests, including earthworm mortality, growth, and reproduction; seedling germination and root elongation; microbial respiration; and nematode mortality and reproduction. Nineteen municipal wastewater treatment plants were identified to participate in an initial screening of toxicity, and five were chosen for a more detailed evaluation. In addition, two soils with historically high applications of high-metal biosolids were evaluated. Contaminants examined were zinc, copper, nickel, chromium, arsenic, cadmium, lead, and coplanar polychlorinated biphenyls (PCBs). Single applications had no effect on soil metal concentrations. Coplanar PCBs were not detectable in any of the soils or biosolids. All target organisms were sensitive to reference toxicants. Limited toxicity was observed in a small number of the amended soils, but no patterns emerged. Approximately one-half of the negative effects of biosolids on bioindicators could be attributed to routine properties, such as slight depression of pH and/or elevated salinity. None of the accumulated metal concentrations were excessive, and most would not be considered elevated. These observations suggest that current regulations for application of biosolids to soils are providing adequate ecosystem protection.     

Characterization of odor released during handling of swine slurry: Part II. Effect of production type,storage and physicochemical characteristics of the slurry

The quality of rural life can be affected by offensive odors released from animal buildings and storage units. The objectives of this study were to compare the concentrations of odor and odorants above different types of stirred swine slurry to analyze the relationships between concentrations of odor (and odorants) and physicochemical characteristics of the slurry (i.e. pH, temperature, dry matter, volatile solids, and concentration of 22 chemical compounds); and to propose predictive models for the odor concentration (OC) based on these physicochemical characteristics (solely and in combination with concentrations of specific odorants in the air above the slurries). The study comprised data on concentrations of odor and odorants in the air above slurry samples (fresh and/or stored) collected from production units with farrowing sows, finishing swines, or weaning pigs at eight swine operations (N = 48). OC measured in the air above stirred swine slurry samples were not significantly different among production types or storage times. The physicochemical characteristics of the slurries were not useful for predicting OC or concentrations of hydrogen sulfide (or organic sulfides) above the slurry, but were related to concentrations of other emitted gases such as phenols and indoles (r² = 0.65–0.79, p <0.05), ammonia (r² = 0.86, p < 0.05) and carboxylic acids (r² = 0.23–0.59, p <0.05). There was good precision of predictive models of OC based on selected slurry characteristics (i.e. pH, dry matter, nitrogen content, sulfur content or concentrations of individual aromatic compounds and carboxylic acids) together with concentrations of specific odorants in the air (e.g. hydrogen sulfide) (r² between 0.70 and 0.92). This study suggests that predictive models could be useful for evaluating odor nuisance potentials of swine slurry during handling.     

Influence of earthworm mucus and amino acids on tomato seedling growth and cadmium accumulation

The effects on the growth of tomato seedlings and cadmium accumulation of earthworm mucus and a solution of amino acids matching those in earthworm mucus was studied through a hydroponic experiment. The experiment included four treatments: 5 mg Cd L⁻¹ (CC), 5 mg Cd L⁻¹ + 100 mL L⁻¹ earthworm mucus (CE), 5 mg Cd L⁻¹ + 100 mL L⁻¹ amino acids solution (CA) and the control (CK). Results showed that, compared with CC treatment, either earthworm mucus or amino acids significantly increased tomato seedling growth and Cd accumulation but the increase was much higher in the CE treatment compared with the CA treatment. This may be due to earthworm mucus and amino acids significantly increasing the chlorophyll content, antioxidative enzyme activities, and essential microelement uptake and transport in the tomato seedlings. The much greater increase in the effect of earthworm mucus compared with amino acid treatments may be due to IAA-like substances in earthworm mucus.     

Effects of alkaline dust deposits from phosphate fertilizer production on microbial biomass and enzyme activities in grassland soils

Microbial biomass carbon (Cmic) and soil enzyme activities were measured at 12 sites along a gradient of former emissions of phosphate fertilizer production. Seven years after close down of operation, still moderate to high total concentrations of the dust constituents cadmium (up to 33 mg kg-1 dw), fluoride (5300 mg kg-1 dw) and phosphorous (120,000 mg kg-1 dw) were found in topsoils of contaminated sites. Accumulation of partially decomposed plant matter, soil respiration and dehydrogenase activity paralleled the increase of dust deposits, whereas microbial biomass decreased along the gradient. A significant negative correlation was obtained between the Cmic-to-Corg-ratio and the concentration of contaminants. In contrast, the Cmic-specific respiration (qCO2) and the dehydrogenase activity-to-Cmic-ratio were positively correlated. The low Cmic-values and the enhanced activities in the contaminated soils are suggested as a response of microbial communities to environmental stress or ecosystem disturbances. The apparently missing detrimental effects of the alkaline deposits on soil microbial activities are probably due to the low bioavailability of contaminants in the calcareous soil.     

The effect of lindane on nucleic acids, protein and carbohydrate content in Tetrahymena pyriformis

The effects of four lindane concentrations, i.e. 20, 40, 60 and 80 microg ml(-1), on the nucleic acid, protein and carbohydrate content of Tetrahymena pyriformis have been examined. All the test concentrations inhibited the synthesis of DNA, RNA, protein and carbohydrate contents. The degree of inhibition increased with increasing toxicant concentrations. Protein content was the most sensitive macromolecule affected by lindane.     

Antioxidant activity and enzyme inhibitory potential of Euphorbia resinifera and E. officinarum honeys from Morocco and plant aqueous extracts

Natural products may be applied in a wide range of domains, from agriculture to food and pharmaceutical industries. In this study, the antioxidant properties and the capacity to inhibit some enzymatic activities of Euphorbia resinifera and Euphorbia officinarum aqueous extracts and honeys were assessed. The physicochemical characteristics were also evaluated. Higher amounts of iron, copper and aluminium were detected in E. officinarum honey, which may indicate environmental pollution around the beehives or inadequate storage of honey samples. This honey sample showed higher amounts of total phenols and better capacity for scavenging superoxide anion free radicals and DPPH free radicals as compared with E. resinifera honey, but poorer capacity for inhibiting lipoxygenase, acetylcholinesterase, tyrosinase and xanthine oxidase. The ratio plant mass:solvent volume (1:100) and extraction time (1 - 2 h) were associated with higher total phenols and better antioxidant activities and lipoxygenase, acetylcholinesterase and tyrosinase inhibitory activities, regardless of the plant species. The aqueous extracts had systematically higher in vitro activities than the respective honey samples.

     

Emissions of ammonia, hydrogen sulfide, and odor before, during, and after slurry removal from a deep-pit swine finisher

It is a common practice in the midwestern United States to raise swine in buildings with under-floor slurry storage systems designed to store manure for up to one year. These so-called "deep-pit" systems are a concentrated source for the emissions of ammonia (NH3), hydrogen sulfide (H2S), and odors. As part of a larger six-state research effort (U.S. Department of Agriculture-Initiative for Future Agriculture and Food Systems Project, "Aerial Pollutant Emissions from Confined Animal Buildings"), realtime NH3 and H2S with incremental odor emission data were collected for two annual slurry removal events. For this study, two 1000-head deep-pit swine finishing facilities in central Iowa were monitored with one-year storage of slurry maintained in a 2.4 m-deep concrete pit (or holding tank) below the animal-occupied zone. Results show that the H2S emission, measured during four independent slurry removal events over two years, increased by an average of 61.9 times relative to the before-removal H2S emission levels. This increase persisted during the agitation process of the slurry that on average occurred over an 8-hr time period. At the conclusion of slurry agitation, the H2S emission decreased by an average of 10.4 times the before-removal emission level. NH3 emission during agitation increased by an average of 4.6 times the before-removal emission level and increased by an average of 1.5 times the before-removal emission level after slurry removal was completed. Odor emission increased by a factor of 3.4 times the before-removal odor emission level and decreased after the slurry-removal event by a factor of 5.6 times the before-removal emission level. The results indicate that maintaining an adequate barn ventilation rate regardless of animal comfort demand is essential to keeping gas levels inside the barn below hazardous levels.     

Effects of pH, organic acids, and inorganic ions on lead desorption from soils

The desorption characteristics of lead in two variable charge soils (one developed from Arenaceous rock (RAR) and the other derived from Quaternary red earths (REQ)) were studied, and the effects of pH value, organic acid, and competitive ions were examined. Desorption of Pb(2+) decreased from nearly 100.0 to 20.0% within pH 1.0-4.0 in both soils, and then the decrease diminished at pH > 4.0. Organic ligands at relatively low concentrations (< or =10(-3) mol L(-1)) slightly inhibited Pb(2+) desorption, but enhanced Pb(2+) desorption at higher concentrations. In this study, citric acid or acetic acid at higher concentrations (>10(-3) mol L(-1)) had the greatest improvement of Pb(2+) desorption, followed by malic acid; and the smallest was oxalic acid. Desorption of the adsorbed Pb(2+) increased greatly with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Pb(2+) desorption more than Zn(2+) at the same loading.     

污水中溶解游离氨基酸和结合氨基酸测定方法研究

采用邻苯二甲醛作为柱前衍生化试剂,结合反相高效液相色谱,对污水中溶解游离氨基酸（dissolvedfreeami．nOacid,DFAA）进行定性和定量分析,探讨了污水样品有无前处理对DFAA分析的影响,并采用气相酸水解方法对污水中总溶解氨基酸（dissolvedtotalaminoacid,DTAA）进行了分析。结果表明,污水经过pH调节和N,流清洗后,可以明显去除氨和挥发性胺的干扰,色谱峰更加清晰;前处理后的水样经RP—HPLC分析,能够快速检测出14种氨基酸,各氨基酸在一定线性范围内呈现良好的线性关系,相应的线性相关系数（R^2）均大于0．99,加标回收率为92％～102％。污水处理厂进水和出水中氨基酸主要以溶解结合氨基酸（dissolvedcombinedaminoacid,DCAA）为主,与进水相比,出水中DFAA含量减少了0．22μmol／L,DTAA由5．68μmol／L降至3．08μmol／L。