Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

铁盐和铝盐混凝对印染废水生化出水中溶解性有机污染物的去除特性

以三氯化铁和硫酸铝为混凝剂,印染废水二级生化出水为研究对象,并利用XAD-8/XAD-4吸附树脂联用技术将印染废水生化出水中溶解性有机物分为疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物,通过小试实验探讨了2种混凝剂对生化出水中各类溶解性有机物的去除效果及特点。实验结果表明,对于该印染废水的生化出水,溶解性有机物的主要成分是疏水性物质,以DOC表征时占总DOC的75%,其中疏水酸约占41%,疏水性物质也是引起色度的主要物质,所占比例以ADMI7.6表征时为89%,其中以非酸疏水物质的贡献最大,达到52%,并且非酸疏水物质中不饱和双键或芳香环有机物的含量较高。在三氯化铁和硫酸铝各自最佳的混凝条件下,均能够有效去除由疏水性物质（疏水酸和非酸疏水物质）引起的色度,但三氯化铁对弱疏水性物质以及亲水物质的去除率高于硫酸铝,这使得三氯化铁对印染废水生化出水中的溶解性有机物的去除效果优于硫酸铝。并且三氯化铁和硫酸铝混凝工艺均能明显降低生化出水的毒性。     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Dissolved oxygen and dietary phosphorus modulate utilization and effluent partitioning of phosphorus in rainbow trout (Oncorhynchus mykiss) aquaculture

Phosphorus (P) is the limiting nutrient in freshwater primary production, and excessive levels cause premature eutrophication. P levels in aquaculture effluents are now tightly regulated. Increasing our understanding of waste P partitioning into soluble, particulate, and settleable fractions is important in the management of effluent P. When water supply is limited, dissolved oxygen concentration (DO) decreases below the optimum levels. Therefore, we studied effects of DO (6 and 10mg/L) and dietary P (0.7 and 1.0% P) on rainbow trout growth, P utilization, and effluent P partitioning. Biomass increased by 40% after 3 weeks. DO at 10mg/L significantly increased fish growth and feed efficiency, and increased the amount of P in the soluble fraction of the effluent. Soluble effluent P was greater in fish fed 1.0% P. DO increases fish growth and modulates P partitioning in aquaculture effluent.     

Effects of solar radiation on the fluorescence properties and molecular weight of fulvic acids from pulp mill effluents

The pulp and paper industry generates large volume of wastewater that adversely affects water resources. Lignin derived macromolecular compounds, similar to natural humic substances, are the main waste products in the pulp mill effluents. The UV-Vis and fluorescence spectroscopies were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. Solar irradiation of the solutions of these fulvic acids caused solution acidification and decay both in the UV-Vis absorbance and in the fluorescence. This decay was not the same for the whole spectra but pointed to the selective photodegradation of lignin typical structures. Furthermore, by sequential ultrafiltration it was found that during irradiation, the high-molecular weight fractions were destroyed and low-molecular-weight constituents, potentially more able to penetrate the cell membranes of living organisms were formed. Photodegradation of macromolecular organic matter from a kraft pulp mill effluent may be a key process occurring in natural waters that modifies the physicochemical properties of such effluents.     

Poly (ε-caprolactone) as substrate for water denitrification

In this paper, poly (ε-caprolactone) (PCL) was used as carbon source and biofilm supporter in a fixed bed bioreactor to biologically remove nitrate from drinking water. The experimental results showed that denitrifying microorganisms could easily adapt to PCL as carbon source and attach to the surface of PCL granules. The fine biofilm could form on the surface of PCL granules within 15 days. Denitrification rate was influenced by temperature greatly and it decreased sharply at low temperature (below 20°C) and it was strongly linearly correlated with influent DO level. The denitrification rate at DO 8.5 mg/L was 47.4% of the value at DO 1.4 mg/L. Fixed-bed bioreactor packed with PCL granules could remove 50 mg/L influent nitrate completely, but the effluent DOC and suspended matter level were high. Accordingly, post-treatment unit are needed to ensure the good quality of effluent. Nitrite level did not accumulate in the whole experiment. Microbial growth was the main reason for reactor clog.     

Effects of an industrial effluent on plant colonization and on the germination and post-germinative growth of seeds of terrestrial and aquatic plant species

Major oil sands industrial companies are located in the Athabasca Oil Sands Deposit in northeastern Alberta, Canada. During the process used to extract light crude oil (via hot water digestion and flotation), gypsum is usually added to produce consolidated tails (CT) and CT release water. The vast volumes of process-treated waters (effluent) are held within large dyked tailings ponds. Toward testing viable options for reclamation, various hummock-wetlands systems have been constructed; in addition, natural wetlands (inhabited by obligate wetland plant species) have become established as a result of seeping of the effluents held within the large dyked ponds. Vegetation surveys conducted on and around the industrial site revealed that the constructed wetlands associated with the dyke drainage (effluent treated with phosphorous) and consolidated tails (CT; effluent treated with gypsum) had low biodiversity and were not invaded by many aquatic plants. Although the natural wetland was also not invaded by many aquatic species, it was found to be as diverse as the reference wetlands (i.e. off-site wetlands not exposed to the effluents). Exposure to oil sands effluents had an inhibitory effect on the germination (percent and/or rate) of several plant species (tomato, clover, wheat, rye, pea, reed canary grass, loblolly pine); clover and tomato seed germination were most affected. Two treatments in particular (effluents from the natural on-site wetland and the CT constructed wetland), delayed germination, and also led to reduced fresh weight of seedlings of tomato, wheat, clover and loblolly pine. The osmolarities of the effluents associated with the natural on-site wetland and CT constructed wetland were 712 and 728 mOs/kg, respectively; substituting these effluents with solutions of polyethylene glycol of the same osmotic potentials had a greater inhibitory effect on germination rate. The negative effects of the effluents on seed germination may account for the paucity of aquatic species that invaded the oil sands impacted wetlands. This factor will also be critical in determining the long-term feasibility of hummock-wetland systems.     

Influence of algal organic matter on metal accumulation in adjacent sediments of aquaculture from a tropical coast region

The rapid development of coastal aquaculture in recent decades has led to excessive discharge of organic matter and nutrients into surrounding waters, which could result in eutrophication and potentially affect metal cycling. In our study, the influence of algal organic matter on metal accumulation was examined in three coastal sediment cores taken from a tropical region, Hainan Island, China. Overall, metal pollution adjacent to aquaculture ponds remained at low levels on the coast, except Zn, Cd, and Sn were moderately to highly enriched in the Dongjiao sediments. The δ¹³C values and the atomic C/N ratios indicated a major contribution of phytoplankton to sedimentary organic matter at the Dongjiao site. Moreover, both the algae-derived organic matter and effluent nitrogen were significantly associated with the enriched Zn, Cd, and Sn, suggesting that nutrient-induced phytoplankton growth and its organic matter may act as a “biological pump” to enhance the accumulation of metals. Wastewater treatment for aquaculture ponds should include the control of algal organic matter.

     

Electrolytic treatment of an industrial wastewater from a hosiery plant.

Textile plant wastewater being treated in a facultative pond system had too high of a solids concentration to be reused in the dying and rinsing processes. Electrocoagulation was evaluated to further treat the pond effluent to remove turbidity, which was caused by dyes and microorganisms. A range of amperages were tested for removal of turbidity and chemical oxygen demand (COD). Electrocoagulation lowered the turbidity from 1400 NTU to below 50 NTU; and COD was lowered from 550 mg/L to approximately 250 mg/L, which was acceptable for reuse. In addition, a laboratory-scale sedimentation study was conducted on the electrocoagulated pond effluent, which indicated that a settling time of 35 minutes would provide for 80% removal of suspended solids, which was acceptable for reuse of the water in plant processes.     

Treatment of bleach pulp mill effluent by MF-MBR

The types of treatment most commonly used by pulp mills are biological treatments in combination with sedimentation or coagulation/flocculation as pretreatment. The main issues faced by these types of treatment are low efficiency in the removal of organic matter and the loss of aggregate value for the recovered fiber. Therefore, this study aims to evaluate the use of microfiltration (MF) combined with a membrane bioreactor (MBR) for the treatment of bleach pulp mill effluents. The results showed that the use of the MF-MBR system was an excellent alternative for the treatment of bleach pulp mill effluents with an average COD removal of 95%. The microfiltration allowed the recovery of fibers, which can be returned to the production process without losing economic value, and produced a better quality effluent for further treatment in the MBR. The MBR presented high efficiency removal of organic matter.     

Chemical modifications of groundwater contaminated by recharge of treated sewage effluent

Long-term monitoring of the chemical composition of recharge sewage effluent and associated contaminated groundwater from the Dan Region Sewage Reclamation Project shows, after 16 years of recharge operation, the presence of a distinct saline plume (up to 400 mg/l Cl), extending 1600 m downgradient in the Coastal Plain aquifer of Israel. The recorded electrolyte composition of groundwater in the vicinity of the recharge area reflects the variations in the compositions of the sewage effluents, as well as water-rock interactions induced by the recharge of treated sewage effluents. The original sewage composition was modified, particularly during early stages of effluent migration in the unsaturated zone, by cation-exchange and adsorption reactions. Since the soil sorption capacity is finite these reactions caused only limited modifications, and once the system reached a steady state the inorganic composition of the contaminated groundwater became similar to that of the recharge water. Decomposition of organic matter in the unsaturated zone resulted in CO₂ generation and dissolution of CaCO₃ minerals in the aquifer. It was shown that chemical and/or bio-degradation of organic matter takes place mainly in the unsaturated (vadose) zone. Hence, monitoring the efficiency of the vadose zone to retain contaminants is essential for evaluating the quality of groundwater since it was shown that organic compounds behave almost conservatively once the effluents enter and flow within the saturated zone.     

Experimental design of Fenton and photo-Fenton reactions for the treatment of cellulose bleaching effluents

Multivariate experimental design was applied to the treatment of a cellulose conventional bleaching effluent in order to evaluate the use of the Fenton reagent under solar light irradiation. The effluent was characterised by the general parameters total organic carbon (TOC), chemical oxygen demand and color, and it was analysed for chlorinated low molecular weight compounds using GC–MS. The main parameters that govern the complex reactive system: Fe(II) and H₂O₂ initial concentration, and temperature were simultaneously studied. Factorial experimental design allowed to assign the weight of each variable in the TOC removal after 15 min of reaction. Temperature had an important effect in the organic matter degradation, especially when the ratio of Fenton reagents was not properly chosen. Fenton reagent under solar irradiation proved to be highly effective for these types of wastewaters. A 90% TOC reduction was achieved in only 15 min of treatment. In addition, the GC–MS analysis showed the elimination of the chlorinated organic compounds initially detected in the studied bleaching effluents.     

Ammonia removal from facultative pond effluents in a constructed wetland and an aerated rock filter: performance comparison in winter and summer.

The effluent from a facultative pond loaded at 80 kg BOD ha(-1) day(-1) was treated in a subsurface horizontal-flow aerated rock filter (RF) and a subsurface horizontal-flow constructed wetland (CW) planted with Typha latifolia. Over a 12-month monitoring period BOD and TSS removals were higher, and effluent ammonia concentrations lower, in the RF than in the CW (> 75% vs. 25-75%, and 3.6 mg N L(-1) vs. 6 mg N L(-1), respectively). However, the ammonia concentration was lower in the CW effluent than in the aerated RF effluent during mid-July to mid-September (1.1 mg N L(-1) vs. 2.2 mg N L(-1)), but in winter it was higher than the influent concentration. Overall the performance of the aerated RF was better and more consistent than that of the CW.     

Chemical status of selenium in evaporation basins for disposal of agricultural drainage

Evaporation basins (or ponds) are the most commonly used facilities for disposal of selenium-laden saline agricultural drainage in the closed hydrologic basin portion of the San Joaquin Valley, California. However concerns remain for potential risk from selenium (Se) toxicity to water fowl in these evaporation basins. In this study, we examined the chemical status of Se in both waters and sediments in two currently operating evaporation pond facilities in the Tulare Lake Drainage District. Some of the saline ponds have been colonized by brine-shrimp (Artemia), which have been harvested since 2001. We evaluated Se concentration and speciation, including selenate [Se(VI)], selenite [Se(IV)], and organic Se [org-Se or Se(-II)] in waters and sediment extracts, and fractionation (soluble, adsorbed, organic matter (OM)-associated, and Se(0) and other resistant forms) in sediments and organic-rich surface detrital layers from the decay of algal blooms. Selenium in ponds without vascular plants exhibited similar behavior to wetlands with vascular plant present, indicating that similar Se transformation processes and mechanisms had resulted in Se immobilization and an increase of reduced Se species [Se(IV), org-Se, and Se(0)] from Se(VI)-dominated input waters. Selenium concentrations in most pond waters were significantly lower than the influent drainage water. This decrease of dissolved Se concentration was accompanied by the increase of reduced Se species. Selenium accumulated preferentially in sediments of the initial pond cell receiving drainage water. Brine-shrimp harvesting activities did not affect Se speciation but may have reduced Se accumulation in surface detrital and sediments.     

Assessment of human health risks and pollution index for heavy metals in farmlands irrigated by effluents of stabilization ponds

Areas contaminated with heavy metals can pose major risks to human health and ecological environments. The aims of this study are to assess human health risk and pollution index for heavy metals in agricultural soils irrigated by effluents of stabilization ponds in Birjand, Iran. The results revealed that the levels of Cr, Mn, Zn, Fe, Cu, Cd, and Pb were in range of 70.3–149.65, 355–570, 31.15–98.45, 23,925–29,140, 22.75–25.95, 0.17–6.51, and 8.5–23.5 mg/kg in topsoils, respectively. Total hazard index values from heavy metals through three exposure routes for adults and children were 9.13E−01 and 1.10, respectively, indicating that there was non-carcinogenic risk for children. The total risk of carcinogenic metals (Cr, Cd, and Pb) through the three exposure routes for adults and children was 1.06E−04 and 9.76E−04, respectively, which indicates that the metals in the soil will not induce carcinogenic risks to these age groups. Pollution levels of heavy metals in soil samples including enrichment factor (EF), contamination factor (CF), pollution load index (PLI), and geo-accumulation index (Igeo) showed heavy metal contamination of agricultural soils. The results of the present study provide basic information about heavy metal contamination control and human health risk assessment management in the study area.     

Evaluation of ion exchange resins for the removal of dissolved organic matter from biologically treated paper mill effluent

In this study, the efficiency of six ion exchange resins to reduce the dissolved organic matter (DOM) from a biologically treated newsprint mill effluent was evaluated and the dominant removal mechanism of residual organics was established using advanced organic characterisations techniques. Among the resins screened, TAN1 possessed favourable Freundlich parameters, high resin capacity and solute affinity, closely followed by Marathon MSA and Marathon WBA. The removal efficiency of colour and lignin residuals was generally good for the anion exchange resins, greater than 50% and 75% respectively. In terms of the DOM fractions removal measured through liquid chromatography–organic carbon and nitrogen detector (LC–OCND), the resins mainly targeted the removal of humic and fulvic acids of molecular weight ranging between 500 and 1000 g mol^?1, the portion expected to contribute the most to the aromaticity of the effluent. For the anion exchange resins, physical adsorption operated along with ion exchange mechanism assisting to remove neutral and transphilic acid fractions of DOM. The column studies confirmed TAN1 being the best of those screened, exhibited the longest mass transfer zone and maximum treatable volume of effluent. The treatable effluent volume with 50% reduction in dissolved organic carbon (DOC) was 4.8 L for TAN1 followed by Marathon MSA – 3.6 L, Marathon 11 – 2.0 L, 21K-XLT – 1.5 L and Marathon WBA – 1.2 L. The cation exchange resin G26 was not effective in DOM removal as the maximum DOC removal obtained was only 27%. The resin capacity could not be completely restored for any of the resins; however, a maximum restoration up to 74% and 93% was achieved for TAN1 and Marathon WBA resins. While this feasibility study indicates the potential option of using ion exchange resins for the reclamation of paper mill effluent, the need for improving the regeneration protocols to restore the resin efficiency is also identified. Similarly, care should be taken while employing LC–OCND for characterising resin-treated effluents, as the resin degradation is expected to contribute some organic carbon moieties misleading the actual performance of resin.     

Formation of chlorinated disinfection by-products in viticulture

Background, aim and scope  The use of sodium hypochlorite (HYP) in viticulture results in effluents which are contaminated with halogenated substances. These disinfection by-products (DBPs) can be quantified as group parameter ‘adsorbable organic halogens’ (AOX) and have not been determined in effluents of viticulture yet. The substances that are detected as AOX are unknown. The AOX can be composed of harmless substances, but even toxic contaminants. Thus, it is impossible to assess ecological impacts. The aim of this study is to determine the quantification of AOX and DBPs after the use of HYP. This will be helpful to reduce environmental pollution by AOX. Materials and methods  The potential of HYP to generate AOX was determined in laboratory-scale experiments. Different model solutions were treated with HYP according to disinfection processes in viticulture and conditions of AOX formation in effluents were simulated. AOX were quantified using the flask-shaking method and identified DBPs were investigated by gas chromatography–mass spectrometry. Results  Treatment with HYP resulted in the formation of AOX. The percentage conversion of HYP to AOX was up to 11%. Most important identified DBPs in viticulture are chloroform, dichloroacetic acid and trichloroacetaldehyde. In addition, the formation of carbon tetrachloride (CT), 1,1,1-trichloropropanone, 2,4-dichlorobenzoic acid and 2-chloro-/2,4-dichlorophenylacetic acid was investigated. It was demonstrated that reaction temperature, concentration of HYP and type of organic matter have important influence on the formation of chlorinated DBPs. Discussion  The percentage conversion of HYP to AOX was similar to other published studies. Although a correlation of single compounds and AOX is difficult, chloroform was the predominant AOX. Generation of the volatile chloroform should be avoided due to possible adverse effects. The generation of dichloroacetic acid is of minor importance on account of biodegradation. Trichloroacetaldehyde and 1,1,1-trichloropropanone are weak mutagens and their formation should be avoided. Conclusions  The generation of AOX and chlorinated DBPs can be minimised by reducing the concentrations of the organic materials in the effluents. The removal of organic matter before disinfection results in a decreased formation of AOX. HYP is an effective disinfectant; therefore, it should be used at low temperatures and concentrations to reduce the amount of AOX. If possible, disinfection should be accomplished by the use of no chlorine-containing agents. By this means, negative influences of HYP on the quality of wine can also be avoided. Recommendations and perspectives  Our results indicate that HYP has a high potential to form AOX in effluents of viticulture. The predominant by-products are chloroform, dichloroacetic acid and trichloroacetaldehyde. In further research, wastewaters from a winery and the in- and outflows of two sewage treatment plants were sampled during vintage and analysed. These results will be discussed in a following paper.     

高效藻类塘氮磷去除机理的研究进展

首先介绍了高效藻类塘的发展历史和特点,其次简述了高效藻类塘的生物特性和物理化学变化规律,并重点论述了高效藻类塘的氮磷去除机理及其影响因素,最后对高效藻类塘在控制非点源污染中的应用前景进行展望.     

Removal of estrone, 17α-ethinylestradiol,and 17ß-estradiol in algae and duckweed-based wastewater treatment systems

Background, aim, and scope  

Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). Because of possible ecological effects and increased attention for water reuse schemes, it is important to increase our understanding of the EDC removal capacities of various wastewater treatment systems. However, there has so far been little research on the fate and behavior of EDCs in stabilization pond systems for wastewater treatment, which represent an important class of wastewater treatment systems in developing countries because of their cost-effectiveness. The aim of this work is to study the fate and behavior of EDCs in algae and duckweed ponds. Because the synthetic hormone 17α-ethinylestradiol (EE2) and the natural hormones estrone (E1), as well as 17β-estradiol (E2), have been detected in effluents of sewage treatment plants and been suggested as the major compounds responsible for endocrine disruption in domestic sewage; E1, E2, and EE2 were therefore chosen as target chemicals in this current work.     

高效藻类塘氮磷去除机理的研究进展

首先介绍了高效藻类塘的发展历史和特点，其次简述了高效藻类塘的生物特性和物理化学变化规律，并重点论述了高效藻类塘的氮磷去除机理及其影响因素，最后对高效藻类塘在控制非点源污染中的应用前景进行展望。