Content: A combination of processing techniques and speciality chemicals has been developed to target environmental issues and legislation in the European leather industry, especially for automotive upholstery leather. This process combines new techniques in the beamhouse process through to the tanning process. Initial work on several different individual concepts showed some excellent improvements, but when these concepts have been brought together to form a single strategic process the advantages and improvements have exceeded expectations. The process demonstrates a reduction in the use of salt, formic acid and sulphuric acid. After more than two years of trials from small scale to full production in an automotive leather production environment, we are able to present independently test results showing the benefits of following this system. Briefly these include Improvement in tear and tensile strength results. Improved clarification with less suspended solids in the supernatant. Reduced COD in the supernatant and higher biodegradability COD/BOD. Less TDS in the supernatant. Chloride content reduction in the supernatant Sludge generation reduction. Less organic residues derived from the hide. Take-Away: A simple technique and small modifications to existing processing methods will reduce dramatically the environmental effects of wet white / chrome free tanning. This process can be used in any country in the world and answers many questions regarding reducing salt, BOD, COD, TDS etc.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22767号 / 工博第4766号 / 新制||工||1745(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 米田 稔, 教授 清水 芳久, 准教授 松井 康人 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Magister Scientiae (Biodiversity and Conservation Biology) - MSc (Biodiv and Cons Biol) / The study illustrates the current ecological integrity of the Diep River system, based on the recent river health assessment using the South African Scoring System version 5 (2000-2003) and the water quality data (1996-2002). Some of the major land-use impacts on the river system are highlighted.

This study discusses the monitoring requirements of an effluent credit trading system that allows point source discharges to purchase effluent reductions by financing agricultural nonpoint source best management practices. It describes the results of a national survey of existing trading programs that assessed how each program determines nonpoint source baseline pollutant discharges, pollutant reductions attributable to best management practices, verification of best management practice(s) installation and maintenance activities, and how often this verification is performed. This study surveyed the nonpoint source discharge monitoring programs of several of the successful effluent credit trading systems in the U.S. It documents and discusses specific characteristics of nonpoint source pollutant discharge monitoring strategies. Finally, this thesis compares trading program discharge monitoring characteristics to the current Virginia Cost-Share nonpoint source monitoring program. The goal of this study is to recommend elements of a nonpoint source discharge monitoring strategy to the Commonwealth of Virginia that can be used in a trading program of its own. The study shows that the majority of existing effluent credit trading programs use watershed models and land use evaluation algorithms to indirectly monitor nonpoint source pollutant discharges on a watershed basis rather than relying on empirical sampling and analysis activities for individual farms of fields. Monitoring takes a variety of forms to provide the diverse information necessary to indirectly determine nonpoint source discharges. Most trading programs monitoring strategies are no more comprehensive than agricultural cost-share programs even though many stakeholders believe that a trading program's monitoring activities should be exact enough to determine contributions from individual nonpoint sources to support the payments for individual activities. This objection is a barrier to the acceptance of trading programs by the public. A Virginia trading program must enhance its agricultural best management practice cost-share program monitoring practices to track nonpoint source discharges from individual farms or fields to be accepted and successful. / Master of Engineering

The presence of pharmaceuticals in the environment has raised an emerging interest due to the fact that they pose negative environmental impact and health hazards related to long-term toxicity effects. As conventional treatments are not able to totally remove these substances it is necessary to seek for alternative advanced technologies such as oxidation with chlorine dioxide (ClO2). The objective of this master thesis is thus to find the most optimal dose – reaction time of ClO2 for the oxidation and maximum removal of selected environmentally relevant pharmaceuticals. Factorial design and subsequent optimization with MODDE was selected as the best approach to find the optimal dose – time. Batch oxidation tests were conducted on 100mL aliquots treated with ClO2 using wastewater effluent from Henriksdal WWTP. Thereafter solid phase extraction and final determination of pharmaceuticals was carried out on a high performance liquid chromatography- triple quadrupole mass spectrometry (HPLC-MS/MS). Results showed that applying a dose of 5 mg ClO2/L and a reaction time of 10 minutes, it is possible to remove more than a half of the 17 analyzed substances. Besides most of the pharmaceuticals with high and moderate environmental risk, would pose a low risk for the environment after treatment with the optimal ClO2 dose – reaction time. Despite the fact that ClO2 could successfully degrade most environmentally relevant pharmaceuticals, deeper research concerning the formation of toxic by-products after oxidative treatment needs to be done before upscaling this technology to pilot or full scale as a suitable end of pipe technology for pharmaceuticals removal.

Margretelund wastewater treatment plant (WWTP) operated by the water utility Roslagsvatten AB, wasbuilt in 1956 and is located in Åkersberga town, Stockholm County, Sweden. Margretelund WWTP waslast renovated in 1999, and has been operated with the same physical, chemical, and biological processessince then. Due to issues with increased phosphorus emissions connected to increased concentration ofeffluent total suspended solids (TSS), Roslagsvatten would like to optimize the operation of their dissolvedair flotation (DAF) process and the author was tasked to conduct a study about the subject. The specificaim of the study was to propose one method for optimization with available means to reduce effluentTSS concentration during high flow rates for the present DAF process at Margretelund WWTP.Achieving the aim required an historical analysis of Margretelund WWTP’s DAF process and aninvestigation of the effect influent flow rate and effluent recycle rate (ERR) had on effluent TSSconcentration. The increase of effluent TSS was believed to be caused by increased flow rates frominfiltration and inflow (recorded to 32% of total volume the year 2020) affecting the dissolved air flotation(DAF) process.The literature study design parameters for a dissolved air flotation process, specifically the recycle flowpressurization configuration, generated information about which parameters to take into considerationwhen optimizing a DAF unit. Analysis of historic effluent measurements at Margretelund showed that42% of all samples analysed between January 2015 – January 2021 were below 10 mg/l TSS. Eachhistorical increase of surface load has brought a decreased effluent recycle rate (ERR) and consequentlyan increasing percentage of samples exceeding 10 mg/l. A Pearson correlation presented a negativecorrelation with both ERR and surface load in relation to effluent TSS concentration. This resulted inthe selection of the experimental factors ERR and surface load to be investigated in this study.Margretelunds WWTP’s DAF design of ERR being 10-15% and the design surface load of 4 m/h wasthe base values for the experimental runs. Increases of ERR percentage was done during the experimentfor four different surface loads (2.5, 4, 5 and 6 m/h), with five steps between 15% up to 35% ERR inone of the three parallel DAF units in Margretelund WWTP. TSS in the effluent was constantlymonitored using a TSS sensor. Influent TSS was measured at Roslagsvatten’s accredited laboratory in a24h composite sample with 1 hour for each sub-sample.The results showed that both the highest and the lowest ERR settings tested provided the lowest averageeffluent TSS concentrations. However, a decreased surface load was found to lower effluent TSSconcentration and ERR providing only minor differences within each surface load. Largest surface loadpossible was found to be 5 m/h, for an ERR of 15 or 35%. Surface load less than 5 m/h provided aconcentration under 10 mg/l for all ERR setting. / Margretelund avloppsreningsverk (ARV) placerat i Åkersberga, Stockholms län, byggdes 1956 och drivs av Roslagsvatten AB. Margretelund ARV har sedan 1956 renoverats vid två tillfällen senast 1999. Samma reningsprocess för fysisk, kemisk och biologisk rening har använts sedan senaste renoveringen. Roslagsvatten har haft problem med oönskat tillskottsvatten (motsvarade 32% av total volym 2020) som har påverkat deras flotationsprocess negativt gällande rening av suspenderat material. Detta har till slut lett till förhöjda utsläppsvärden av fosfor som finns bundet i det suspenderade materialet. Denna studie har utförts av författaren på efterfrågan av Roslagsvatten, med syfte att presentera optimeringsåtgärder till styrning av flotationsprocessen vid höga flöden. För att uppnå målet med studien gjordes en historisk analys av Margretelunds flotationsprocess samt undersökningar om hur variationer i inkommande flöde samt recirkuleringsgrad har påverkat koncentration av utgående suspenderat material.Teori undersöktes och information insamlades angående designparametrar gällande optimering av flotationsprocesser, mer specifikt en flotationsprocess med recirkulerat trycksatt flöde för avskiljning av susp. Analys av historiska utsläppsvärden från Margretelund ARV’s flotationsprocess visade på att 42% av proverna analyserade mellan januari 2015-januari 2021 låg under 10 mg/l för utgående suspenderat material. Varje historisk ökning av ytbelastning påvisade en minskande recirkuleringsgrad samt en ökande andel prover som översteg koncentrationen 10 mg/l. Utifrån en Pearson korrelation visades en negativ korrelationen för både ytbelastning och recirkulationsgrad gentemot koncentration av utgående suspenderat material. Både recirkuleringsgrad och ytbelastning valdes därför till denna studies experimentella faktorer. Flotationsprocessen på Margretelund ARV’s var designad för en recirkuleringsgrad på 10–15% vid ytbelastning på 4 m/h, och valdes som basvärde för experimentet. Fem olika grader av recirkulation testades för fyra olika ytbelastningar (2.5, 4, 5 och 6 m/h) i intervallet 15–35% i en av tre parallella flotations bassänger på Margretelund ARV. Koncentration utgående suspenderat material mättes kontinuerligt med en sensor. Inkommande koncentration bestämdes genom ett dygnsprov som analyserades av Roslagsvattens ackrediterade laboratorium.Ett resultat från experimenten var att både den högsta och lägsta inställningen av recirkuleringsgrad visade de lägsta medelvärdena för utgående koncentration av suspenderat material. Dock, visade resultaten att en minskande ytbelastning resulterade i lägre koncentrationer av utgående suspenderat material. Vidare sågs att recirkuleringsgraden enbart hade en låg påverkan på koncentrationerna för varje ytbelastning. Den högsta möjliga ytbelastningen utan att överstiga 10 mg/l visades vara 5 m/h med recirkuleringsgraderna 15% och 35%.

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Wastewater reclamation and reuse have been increasingly practiced as sustainable strategies to meet water demands, particularly in regions threatened by water shortages. However, one of the biggest challenges for reusing wastewater effluents (WEs) as irrigation water is to remove emerging organic contaminants such as persistent and potentially bioaccumulated per- and polyfluoroalkyl substances (PFAS), whose presence may result in adverse impacts on crops, soils, aqueous ecosystems, and human health. Photocatalysis is an effective and promising technique to remediate PFAS in aqueous media. This dissertation aims to: i) Develop a novel, environmental-friendly, and low-cost treatment process for PFAS removal and degradation for water reuse; ii) Optimize the experimental conditions and investigate the removal mechanisms of PFAS with different structures in this novel process; iii) Scale up this treatment process and apply it to treatment of WEs in a point-of-use (POU) system. First, ultraviolet (UV) C /nanoscale zero-valent iron (nZVI, Fe0 nanoparticles (NPs)) system is used for the first time to induce PFAS photocatalytic removal from aqueous solution. Oxidative and/or reductive degradation of three representative PFAS - perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS) was achieved using Fe0 NPs under UVC light both with and without presence of oxygen. However, no PFAS removal was observed either under visible light and in the dark, and much lower PFAS degradation was achieved under UVA light. Higher degradation and defluorination efficiencies were obtained for longer chain PFNA compared to PFOA, and higher degradation and defluorination of PFAS were achieved without presence of O2 compared to with O2. The degradation of PFOA and PFOS followed first order reaction kinetics with the highest efficiencies achieved of 97.6, >99.9, and 98.5% without presence of O2 for PFOA, PFNA, and PFOS, respectively. The degradation efficiencies increased with the increase of nZVI concentrations in the range of 1-100 mg/L. The degradation efficiency of PFOA using bare Fe0 NPs was higher than that using 1% PVP-coated Fe0 NPs in the initial 6 h. Second, the removal mechanism of PFAS in UVC/Fe0 NPs system was obtained by testing the concentrations of iron ions (Fe2+/Fe3+), intermediate products, and reactive oxygen species (ROS, e.g., ·O2- and ·OH) generated, and conducting ROS quenching experiments. The proposed degradation pathway of PFCAs (PFNA and PFOA) was initiated from PFOA/PFNA oxidation by transferring an electron of the carboxylate terminal group of PFOA/PFNA to the Fe(III)-carboxylate complex, then followed by decarboxylation−hydroxylation−elimination−hydrolysis (DHEH) pathway and the accompanying CO2 and F− release. The generated shorter chain PFCAs also underwent degradation with time in the system. This proposed degradation pathway was confirmed by the formation of shorter chain PFCAs, e.g. PFHpA, PFHxA, PFPeA, and PFBA, F- ions, and rapid consumption of Fe3+. For PFOS, besides H/F exchange pathway and chain-shortening (DHEH pathway) to form short chain PFAS during PFCA degradation, desulfonation to form PFOA followed by PFOA degradation also happened. These pathways were suggested by the formation of intermediates — trace amount of shorter chain PFCAs, 6:2 FTS, PFHpS, and F- ions. ·O2- and ·OH were not involved in PFOA degradation in the UVC/Fe0 NPs system with presence of O2, while they may be involved in PFOS degradation, e.g., desulfonation to form PFOA, which were suggested by the results of quenching experiments. And introducing H2O2 into the UVC/Fe0 NPs system resulted in lower PFOA degradation efficiency and defluorination efficiency, which also indicated that ·OH may not be involved in PFOA degradation. Hydrated electrons e-aq that can be involved in desulfonation, defluorination, and C-C bond scission processes were likely quenched by the presence of oxygen to reduce the degradation and defluorination efficiencies; plus, presence of Fe0 NPs may promote the generation of hydrated electrons. Last, UVC/Fe0 NPs system was used to degrade PFAS from WEs in both bench scale and in a scale up POU system. The degradation efficiencies of PFAS in WEs from both wastewater treatment plants (WWTP) were lower than that in deionized water, likely reflecting the complex compositions in the environmental media. Optimal degradation efficiencies of 90±1%, 88±1%, and 46±2% were obtained for PFNA, PFOS, and PFOA, respectively, each starting from 0.5 µg/L using bare Fe0 at pH 3.0 after 2 h. PFAS removal and bacterial inactivation were achieved simultaneously in the POU system using Fe0 NPs without and with rGO support under UVC irradiation in WEs, although the PFAS levels were still above the regulation levels for discard. These pilot tests provided more data and experiences for the real applications of UVC/Fe0 NP system to PFAS contaminated wastewater or other water matrix treatment. Overall, this research demonstrated a cost-effective and environment-friendly method — UVC/Fe0 NPs method for PFAS (i.e., PFOA, PFNA, and PFOS) degradation from WEs for water reuse both with and without presence of oxygen. The possible degradation mechanisms of PFAS with different structures were obtained by testing the concentrations of iron ions, intermediate products, and reactive oxygen species (ROS) involved in the reactions. The developed technology can be potentially applied to treat other environmental media (e.g., groundwater, landfill leachate) that are contaminated by PFAS from previous anthropogenic activities.

Microplastics are present in municipal wastewater treatment plant (WWTP) effluents; however, it is unclear whether these contaminants are ingested by biota living downstream of these outfalls. This study examined whether microplastic levels in caged biota, resident fish, and environmental samples were elevated near the Waterloo and Kitchener WWTP outfalls along the Grand River in the fall of 2019. Amphipods (Hyalella azteca), fluted-shell mussels (Lasmigona costata), and rainbow trout (Oncorhynchus mykiss) were caged at one upstream reference site and two impacted sites downstream of the Kitchener WWTP for 14 (amphipods and trout) or 28 (mussels) days. Rainbow darter (Etheostoma caeruleum) were collected using a backpack electrofisher from 10 sites up and downstream of both the Kitchener and Waterloo WWTPs, along with surface water and sediment samples. Whole body Hyalella, fish digestive tracts, and fluted-shell mussel tissues (hemolymph, digestive glands, and gills) were digested in 20% potassium hydroxide. Environmental samples were processed using filtration and density separation, then visual identification of microplastics was done. Elevated particle counts were found in rainbow trout digestive tracts at the Kitchener outfall site, compared to the upstream reference and downstream farfield sites. Additionally, particle concentrations in sediment were significantly higher at the Waterloo outfall, compared to all other sites (except for one upstream location). However, whole Hyalella, fluted-shell mussel tissues (hemolymph, digestive glands, and gills), digestive tracts of rainbow darter, and surface waters did not show elevated counts downstream of these discharges. Across all samples, fibers were the most common morphology, and blue and clear particles were prevalent in samples collected near WWTPs. Overall, these findings suggest that the Kitchener and Waterloo WWTPs could be important sources of particles to the Grand River, adding to our understanding of the fate of this contaminant in freshwater ecosystems. / Thesis / Master of Science (MSc)

Water is an essential and indispensable component is the pulp- and paper production industry.The increase in energy costs, stricter environmental regulations and water resource shortageshave caused a reduction of the water footprint in the industry as well as an increase in waterrecycling and water circuit closure. Reducing water usage requires an understanding of wherecontaminants originate, as well as which streams are critical to the process and how they impactmill operation. The recirculation of water can cause contaminant accumulation; therefore millsemploy technologies for water treatment in the internal water cycles, the so-called ‘kidneys’.Application of membrane technology is one such option which can improve the recycled waterquality and reduce contaminant buildup.The present study was carried out on a lab-scale for the treatment of a tissue mill effluent usingmembrane separation. A combination of pretreatment methods and various membranes werecompared with regards to separation, flux and fouling. The AlfaLaval M20 device was to treatwastewater samples sent from the mill, where the permeate was recirculated to the feed tank.COD and TOC levels are compared with regards to determining the separation efficiency. Thepermeate flux was measured over the two-hour filtration period, as well as flux recovery todetermine fouling levels. Additionally, some economic aspects of the process are discussed.This study suggests the potential application of a combination of flocculation or centrifugationpretreatment, with reverse osmosis membranes for recycling water to replace freshwater intake.The results also indicate the possibility of using ultrafiltration as kidneys to decreasecontamination buildup for further water loop closure.