Eric D. van Hullebusch Editor Bioremediation of Selenium Contaminated Wastewater Bioremediation of Selenium Contaminated Wastewater Eric D. van Hullebusch Editor Bioremediation of Selenium Contaminated Wastewater 123 Editor EricD.vanHullebusch UniversitéParis-Est LaboratoireGéomatériauxetEnvironnement (EA4508), UPEM Marne-la-Vallée France ISBN978-3-319-57830-9 ISBN978-3-319-57831-6 (eBook) DOI 10.1007/978-3-319-57831-6 LibraryofCongressControlNumber:2017947466 ©SpringerInternationalPublishingAG2017 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission orinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped. 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Printedonacid-freepaper ThisSpringerimprintispublishedbySpringerNature TheregisteredcompanyisSpringerInternationalPublishingAG Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland Preface Selenium (Se) is a naturally occurring, semimetallic trace element (Se; atomic number34)thatwasdiscovered200yearsagobytheSwedishchemistsJönsJakob Berzelius (1779–1848) and Johan Gottlieb Gahn (1745–1818). Since then, many studies have been published describing its chemical properties as well as its bio- logicalimportance.Selenium,ifpresentattraceconcentrationlevels,isanessential nutrient in the diets of all living organisms; in excess, however, it is quite toxic. Ontheoccasionofthe200thanniversaryofthediscoveryofselenium,thepresent Springer book entitled “Bioremediation of Selenium Contaminated Wastewater” summarizes the recent advances in this field. Selenium has emerged as a water treatment contaminant deriving from global industrial activities (i.e., coal and mineral mining, metal smelting, oil extraction and refining, and agricultural irriga- tion). Selenium can bioaccumulate in aquatic ecosystems and presents a source of toxicity for many organisms, including humans. However, selenium represents an extremely difficult contaminant to remove from wastewater due to its range of solubility and state of matter (speciation) over different chemical oxidation states mainly influenced by microbial biotransformation reactions (Chapters “Bacterial Metabolism of Selenium—for Survival or Profit” and “Understanding Selenium Biogeochemistry in Engineered Ecosystems: Transformation and Analytical Methods”). Chapter “Bacterial Metabolism of Selenium—for Survival or Profit” aims at presenting timely report of the state of the art regarding the microbial biotransformationofseleniumchemicalspecies.Chapter“UnderstandingSelenium Biogeochemistry in Engineered Ecosystems: Transformation and Analytical Methods” reports on the best analytical techniques allowing to monitor and unra- vel selenium biogeochemical pathways and determine selenium speciation in environmental technologies aiming at the removal of selenium from contaminated wastewaters. Due to increased enforcement of selenium regulations and an increased under- standing of its health and environmental effects, the need to be able to efficiently remove selenium from contaminated effluents has taken on an increased impor- tance. Different treatment approaches may be applied for the removal of selenium from wastewater. This Springer book aims at reporting the recent advances v vi Preface regardingdifferent treatmenttechnologiesthat couldbeimplementedrangingfrom thebiologicalapproach(i.e.,byusingapurebacterialstrain—Chapter“Bioprocess ApproachesfortheRemovalofSeleniumfromIndustrialWasteandWastewaterby Pseudomonas stutzeri NT-I” or by using microbial consortia—Chapter “Industrial Selenium Pollution: Sources and Biological Treatment Technologies”) to the physicochemical approach that is largely applied at industrial scale (Chapter “Industrial Selenium Pollution: Wastewaters and Physical-Chemical Treatment Technologies”).Thesethreewatertreatmenttechnologychaptersaimatprovidinga suitable report of the state of the art regarding the (bio)processes designed for the removal of selenium from contaminated waste streams. These chapters will defi- nitelybringnecessaryinformationwhenoneneedstoimplementawatertreatment process aiming at removing selenium from industrial contaminated effluents. Iwouldliketoconveymyappreciationtoallcontributors.Myspecialthanksto Ms.SofiaCostafromSpringerDEforherkindsupportandgreateffortsinbringing thebooktocompletion.IwouldliketothanktheseriesEditorofSpringerBriefsin Biometals Prof. Larry Barton for inviting me to wrap up all the recent knowledge regardingthe(bio)remediationofseleniumcontaminatedwastewaters.Iamgladto submitthisbook,andIhopethatthereaderswillappreciatereadingthisvolumeas much as I enjoy working on this topic for more than 10 years. Delft, The Netherlands Eric D. van Hullebusch January 2017 Contents Bacterial Metabolism of Selenium—For Survival or Profit.. ..... .... 1 Lucian C. Staicu and Larry L. Barton Understanding Selenium Biogeochemistry in Engineered Ecosystems: Transformation and Analytical Methods. .... .... .... .... ..... .... 33 Rohan Jain, Eric D. van Hullebusch, Markus Lenz and François Farges Bioprocess Approaches for the Removal of Selenium from Industrial Waste and Wastewater by Pseudomonas stutzeri NT-I.. .... ..... .... 57 Michihiko Ike, Satoshi Soda and Masashi Kuroda Industrial Selenium Pollution: Sources and Biological Treatment Technologies .. .... .... .... ..... .... .... .... .... .... ..... .... 75 Lucian C. Staicu, Eric D. van Hullebusch, Bruce E. Rittmann and Piet N.L. Lens Industrial Selenium Pollution: Wastewaters and Physical–Chemical Treatment Technologies.. .... ..... .... .... .... .... .... ..... .... 103 Lucian C. Staicu, Eric D. van Hullebusch and Piet N.L. Lens vii — Bacterial Metabolism of Selenium For fi Survival or Pro t Lucian C. Staicu and Larry L. Barton Abstract Selenium (Se) is transformed by phylogenetically diverse bacteria fol- lowing several basic strategies which include: (1) satisfying a trace element requirement for bacterial synthetic machinery (assimilatory metabolism), (2) cellu- lar energy production coupled to oxidation/reduction reactions (dissimilatory metabolism), and (3) detoxification processes. Some bacteria can use Se for res- piration under limiting anaerobic conditions, generating energy to sustain growth. Under aerobic conditions, Se behaves as a toxicant and bacteria have evolved differentstrategiestocounteractit.Animportantdetoxificationmechanisminvolves the formation of Se nanoparticles with a diminished toxic potential, but the cells have to properly manage these products in order to maintain their integrity. The bacterial metabolism of Se can be regarded as a survival mechanism when Se compoundsprovetobehighlytoxic.Secondly,seleniumisusedtoobtainenergyin anutrient-depleted environment,therefore allowingtospecializedbacterialspecies to prevail over competitors that cannot exploit this resource. To achieve the Se metabolic activities, numerous unique enzymes are employed. While some enzymes have been isolated and are markedly specific for Se, many of the Se enzymes remain to be isolated. The formation of Se nanoparticles inside bacteria and the transportation mechanisms to the extracellular environment are still under debate. Se nanoparticles do not appear to play a nutritional (energy storage) or ecological function for bacteria, being by-products of bacterial metabolism. However, from a biotechnological standpoint, these conversions could be used to (1) clean up industrial effluents rich in Se and (2) to produce biomaterials with industrial applications (biofactory). L.C.Staicu(&) FacultyofAppliedChemistryandMaterialsScience,UniversityPolitehnicaofBucharest, Bucharest,Romania e-mail:[email protected] L.L.Barton DepartmentofBiology,UniversityofNewMexico,Albuquerque,NM,USA e-mail:[email protected] ©SpringerInternationalPublishingAG2017 1 E.D.vanHullebusch(ed.),BioremediationofSeleniumContaminated Wastewater,DOI10.1007/978-3-319-57831-6_1 2 L.C.StaicuandL.L.Barton (cid:1) (cid:1) (cid:1) Keywords Selenium Bacterial metabolism Dissimilatory selenate reduction (cid:1) (cid:1) Selenium toxicity Selenium nanoparticles Biotechnology Abbreviations DSeR Dissimilatory selenate reduction GSH Glutathione M Molar NAD+ Nicotinamide adenine dinucleotide NP Nanoparticle QD Quantum dots ROS Reactive oxygen species Se Selenium Se0 Elemental selenium (zero valence state) Se(IV) Selenite, SeO 2− 3 Se(VI) Selenate, SeO 2− 4 Sec Selenocysteine SefA Selenium factor A SeMet Selenomethionine SeO Selenium oxyanions (selenite and selenate) x SerABC Selenate reductase isolated from Thauera selenatis SOD Superoxide dismutase SRB Sulfate-reducing bacteria 1 Introduction Microbial metabolism of selenium (Se) has only been studied marginally until the late1980smainlyduetoanalyticallimitations.Whatgalvanizedtheresearchonthis topicwasaseriesofenvironmentalpollutioneventshavingSeoxyanions,selenate and selenite, as the causative agents. The first major case occurred in North Carolina(USA)duringthemid-1970s,whenSeleachedfromthecoalashdeposited in the vicinity of Lake Belews eliminated 19 out of 20 fish species (Lemly 2002). Thesecond eventtook place inCalifornia (USA) asaresult ofextensiveirrigation systems that led to the leaching of Se from seleniferous soils to Kesterson Reservoir. The high levels of bioaccumulated Se have been linked to deformities anddeathobservedinthewaterfowlandfishpopulationsofthereservoir,triggering environmental actions (Presser and Ohlendorf 1987; Ohlendorf 1989). These environmental disasters prompted scientists toexplorein more detail themicrobial transformations of Se and their biogeochemical implications. A major finding was the ability of some bacteria to use selenium for anaerobic respiration. This discovery shed light on the biogeochemistry of selenium, and the major contribution played by bacteria in the cycling of this element. The first BacterialMetabolismofSelenium—ForSurvivalorProfit 3 reductase with high affinity for selenium was identified in the periplasmic com- partment ofThaueraselenatis. Apart from theiruseasterminal electron acceptors, selenium compounds can behave as powerful toxicants, but bacteria have evolved differentstrategiestocounteracttheirimpact.Amajorstrategyistheproductionof solid nanoparticles with a significantly lower toxicity. The scientific merits of investigating the bacterial metabolism of selenium consist not only in the eluci- dation of fundamental biogeochemical aspects, but also in the applied side of environmentalresearch(e.g.,thebiologicaltreatmentofindustrialeffluentsandthe production offunctional biomaterials). This chapter discusses the central role of selenate and selenite in the selenium biogeochemical cycle with the formation of Se (nano)particles, both as a detoxi- fication process and as a residual product of the energy generation process. We examinethetoxicity ofSe for bacteriaand different avenuesemployed by bacteria in its detoxification. This review includes an overview of selenium dissimilatory reduction, the transmembrane movement of selenium, selenium stress response of bacteria, and regulatory processes associated with selenium metabolism. This chapter also presents several biotechnological applications founded on bacterial metabolism. 2 Selenium Biogeochemical Cycle Aspartofthechalcogenelements(group16oftheperiodictable),seleniumshares commonpropertieswithsulfur(S)andtellurium(Te).UnlikeSthatisabundantin theEarth’scrust,Seispresentinnano-tomicromolaramountsanditrarelyoccurs in its native state (Kabata-Pendias 2000). In nature, Se is associated with metal-sulfideminerals(e.g.,pyriteandchalcopyrite)andbiolites/sedimentaryrocks ofbiologicorigin(e.g.,coal,oil,andbituminousshales),butcanalsobeenrichedin seleniferous soils (Winkel et al. 2011). Selenium has four oxidation states, (+VI), (+IV), (0), and (−II), that are com- monly observed in biology. A biogeochemical cycle of Se comprising inorganic and organic forms that are transferred through different environmental compart- ments was first proposed by Shrift (1964). Following this seminal article, bacteria were later found to be involved in most transformations undergone by Se (Fig. 1). Similar to S and Te, Se hydrolyzes in aqueous solutions to form oxyanions (SeO ), selenate (Se[+VI], SeO 2−), and selenite (Se[+IV], SeO 2−). Both Se x 4 3 oxyanions are water-soluble, bioavailable, and toxic (Hamilton 2004). Selenium oxyanionsareenvironmentallypersistentasaconsequenceoftheirpH-independent solubility and limited interaction with cations (Chapman et al. 2010). The mech- anism of toxicity is related to the incorporation of Se in sulfur-rich proteins and protein structures (e.g., sulfur-to-sulfur linkages) due to the chemical similarity between the two elements, which results in dysfunctional biomolecules (Stadtman 1974). In addition, selenium poisoning has also been linked to oxidative stress (Hoffman 2002).