Komisja Nauk Towaroznawczych – Nauk o Jakości
przy Oddziale Polskiej Akademii Nauk w Poznaniu
INDEKS ISSN 1733-747XWYDAWCY:
Uniwersytet Technologiczno-Humanistyczny im. K. Pułaskiego ul. Chrobrego 31, 26-600 Radom
TOWAROZNAWCZE
1(5 4)/20 1 8
1 (54)
2018
PROBLEMY JAKOSCI
POLISH JOURNAL OF COMMODITY SCIENCE
T O W AR OZN A W CZE PR OBLEMY JAK OSCI
NAUKI TECHNICZNE NAUKI PRZYRODNICZE
NAUKI EKONOMICZNE
T T
TOWAROZNAWSTWO
1 [54]
2018
Komitet Naukowy/Scientific Committee:
Prof. Jerzy Żuchowski, Uniwersytet Technologiczno-Humanistyczny, Radom, Polska – Przewodniczący Komitetu Naukowego
Prof. Girma Biresaw, United States Department of Agriculture, Peoria, Illinois, USA Prof. Tom Bramorski, University of Wisconsin, Whitewater, Wisconsin, USA Prof. Horst Brezinski, Technische Universität – Bergakademie, Freiberg, Niemcy Prof. Pasquale Giungato, University of Bari, Bari, Włochy
Prof. Marcel Mayor, University of Basel, Szwajcaria
Prof. Mitsuharu Mitsui, University of Okayama, Okayama, Japonia
Prof. Marian W. Sułek, Uniwersytet im. Kardynała Stefana Wyszyńskiego, Warszawa, Polska Prof. Sun Yongqiang, China Research Institute of Daily Chemical Industry, Taiyuan, Shanxi, Chiny Prof. Ryszard Zieliński, Uniwersytet Ekonomiczny, Poznań, Polska
Redaktorzy Naczelni/Editors in Chief:
Dr hab. inż. Tomasz Wasilewski, prof. UTH, Uniwersytet Technologiczno-Humanistyczny w Radomiu Prof. dr hab. inż. Ryszard Zieliński, Uniwersytet Ekonomiczny w Poznaniu
Redaktorzy Tematyczni/Subject Editors:
Towaroznawstwo kosmetyków i produktów chemii gospodarczej – dr hab. inż. Tomasz Wasilewski, prof. UTH
Towaroznawstwo opakowań – prof. dr hab. Małgorzata Lisińska-Kuśnierz Towaroznawstwo przemysłowe – prof. dr hab. inż. Ryszard Zieliński Towaroznawstwo żywności – prof. dr hab. Maria Śmiechowska Zarządzanie jakością – prof. dr hab. inż. Jerzy Żuchowski
Towaroznawstwo wyrobów tekstylnych i odzieżowych, bezpieczeństwo produktów nieżywnościowych – dr hab. inż. Renata Salerno-Kochan, prof. nadzw. UE
Redaktor Statystyczny/Statistical Editor:
Dr hab. Andrzej Sokołowski, prof. UEK Komitet Redakcyjny/Editorial Board:
Dr Anita Bocho-Janiszewska, Uniwersytet Technologiczno-Humanistyczny w Radomiu Prof. dr Pasquale Giungato, Uniwersytet w Bari, “Aldo Moro”
Dr inż. Emilia Klimaszewska, Uniwersytet Technologiczno-Humanistyczny w Radomiu Dr hab. Małgorzata Lotko, Prof. Uniwersytet Technologiczno-Humanistyczny w Radomiu Dr inż. Anna Małysa, Uniwersytet Technologiczno-Humanistyczny w Radomiu
Dr inż. Małgorzata Zięba, Uniwersytet Technologiczno-Humanistyczny w Radomiu Adres Komitetu Redakcyjnego
Uniwersytet Technologiczno-Humanistyczny, ul. Chrobrego 27, 26-600 Radom, tel. (48) 361-75-39; e-mail: tpj@uthrad.pl, www.tpj.uniwersytetradom.pl
Redakcja czasopisma „Towaroznawcze Problemy Jakości” informuje, że formą referencyjną czasopisma jest wersja drukowana.
Publikacje można nadsyłać na adres Komitetu Redakcyjnego ISSN 1733-747X
Wydawcy:
Uniwersytet Technologiczno-Humanistyczny im. K. Pułaskiego, ul. Malczewskiego 29, 26-600 Radom
Instytut Technologii Eksploatacji – PIB, ul. K. Pułaskiego 6/10, 26-600 Radom Opracowanie wydawnicze: Joanna Iwanowska, Iwona Nitek
Wydawnictwo
ul. Malczewskiego 20A, 26-600 Radom, tel. centr. (48) 361-70-33, fax (48) 361-70-34 e-mail: przypis@poczta.onet.pl http://www.uniwersytetradom.pl
Wydawnictwo Naukowe Instytutu Technologii Eksploatacji – PIB
ul. K. Pułaskiego 6/10, 26-600 Radom, tel. centr. (48) 364-42-41, fax (48) 364-47-65
TOWAROZNAWCZE PROBLEMY JAKOŚCI 1(54)/2018
Spis treści
Przedmowa ... 5 Wacław Adamczyk: Innowacje technologiczne w recyklingu koncentratów
cynku ... 11 Artur Jachimowski: Ocena jakości wody w sieci wodociągowej miasta
Krakowa ... 20 Krzysztof Wójcicki: Korelacja pomiędzy widmami w bliskiej podczerwieni
a zanieczyszczeniem sody kalcynowanej przy wykorzystaniu modeli regresji
PLS i PCR ... 37 Malgorzata A. Jarossová: Postawy i wybrane zachowania zakupowe
słowackich konsumentów w odniesieniu do żywności funkcjonalnej
– badania wstępne ... 42 Paulina Witt, Maria Śmiechowska: Ocena jakości sensorycznej jaj z produkcji
ekologicznej i konwencjonalnej ... 51 Anna Dankowska, Dawid Kowalski: Wpływ wybranych sposobów zaparzania
kawy na zawartość kofeiny w naparach kawowych ... 58 Mariusz Jakubowski, Maria Śmiechowska: Charakterystyka jakościowa
kombuchy – nowowoczesnego napoju na bazie fermentowanej herbaty ... 66 Elwira Brodnicka, Maria Szpakowska: Zastosowanie potencjometrycznego
sensora smaku z elektrodami typu ASSE do rozróżniania czerwonych
wytrawnych win z polskich i francuskich winnic ... 76 Paulina Malinowska, Katarzyna Kujałowicz: Analiza oferty rynkowej
kosmetyków przeciwzmarszczkowych przeznaczonych do pielęgnacji
skóry dojrzałej ... 85 Kamila Utracik, Ryszard Zieliński: Ocena właściwości kremów kosmetycznych zawierających oleje z wiesiołka dwuletniego i czarnuszki siewnej ... 94 Daria Wieczorek, Dobrawa Kwaśniewska, Ying-Lien Chen, Tang-Long Shen:
Aktywność przeciwdrobnoustrojowa surfaktantów sulfobetainowych ... 107 Julia Szutowska, Daniela Gwiazdowska: Badania przesiewowe bakterii kwasu
mlekowego będących potencjalnymi producentami biosurfaktantów ... 117 Informacje ... 127
Contents
Preface ... 9 Wacław Adamczyk: Technological innovations in recycling of zinc
concentrates ... 11 Artur Jachimowski: Evaluation of the quality of water in the water supply
network of the city of Krakow ... 20 Krzysztof Wójcicki: Correlation between near infrared spectra and soda ash
contamination using PLS and PCR regression models ... 37 Malgorzata A. Jarossová: Attitudes and selected buying behaviour of Slovak
consumers related to functional foods – preliminary research... 42 Paulina Witt, Maria Śmiechowska: The assessment of the sensory quality
of the eggs from organic and conventional production ... 51 Anna Dankowska, Dawid Kowalski: Impact of selected brewing methods
on caffeine content in coffee infusions ... 58 Mariusz Jakubowski, Maria Śmiechowska: Quality characterization
of Kombucha – newfangled fermented tea beverage ... 66 Elwira Brodnicka, Maria Szpakowska: Application of potentiometric taste
sensor with All Solid State Electrodes for distinguishing of red dry wines
from Polish and French vineyards ... 76 Paulina Malinowska, Katarzyna Kujałowicz: Analysis of a market offer
of anti-wrinkle cosmetics intended for mature skin care ... 85 Kamila Utracik, Ryszard Zieliński: Evaluation of the properties of cosmetic
creams containing evening primrose oil and sapphire oil ... 94 Daria Wieczorek, Dobrawa Kwaśniewska, Ying-Lien Chen, Tang-Long Shen:
Antimicrobial activity of sulfobetaine type surfactants ... 107 Julia Szutowska, Daniela Gwiazdowska: Screening of lactic acid bacteria
as potential producers of biosurfactants ... 117 Information ... 127
P r z e d m o w a
Zgodnie z przyjętym przez Kolegium Redakcyjne długoterminowym planem wy- dawniczym w pierwszych dniach stycznia 2018 roku oddajemy do rąk Państwa – naszych czy- telników – pięćdziesiąty czwarty numer kwartalnika „Towaroznawcze Problemy Jakości”
(Polish Journal of Commodity Science). Kontynuując próby rozszerzenia grona naszych czy- telników wszystkie artykuły publikujemy w angielskiej wersji językowej. Jednocześnie przy- pominamy, że obecnie redakcja kwartalnika przyjmuje do publikacji artykuły przygotowane wyłącznie w języku angielskim. Tak jak poprzednio, każdy artykuł zawiera obszerne stresz- czenie zarówno w języku polskim, jak i angielskim. Streszczenia wszystkich prac opubliko- wanych na łamach kwartalnika w obydwu wersjach językowych dostępne są również na stronie internetowej naszego czasopisma pod adresem: http://www.tpj.uniwersytetradom.pl. Ponadto obecnie na stronie internetowej dostępne są w formule open-access pełne wersje wszystkich artykułów opublikowane na łamach naszego czasopisma do roku 2016 włącznie.
Serię 12 artykułów obecnego wydania naszego czasopisma otwierają dwa dotyczące za- gadnień jakości środowiska. Pierwsza praca dotyczy innowacji technologicznych związanych z realizacją koncepcji zrównoważonego rozwoju. Adamczyk przedstawił innowacje technolo- giczne związane z recyklingiem koncentratów cynku w zakładach produkcyjnych. W pracy poddano analizie proces recyklingu koncentratu cynku z odpadów w zmodyfikowanym proce- sie przewałowym Waelza. Omówiono problemy klasyfikacji uzyskiwanego w tym procesie pełnowartościowego koncentratu cynku w świetle przepisów Ustawy o odpadach oraz reje- stracji REACH.
W drugiej pracy Jachimowski omawia zagadnienie jakości wody pitnej dostarczanej siecią wodociągową miasta Krakowa. Na podstawie analizy kilkuletnich danych doświadczalnych stwierdzono, że jakość wody zależy w głównym stopniu od źródła jej pochodzenia. Wykaza- no, że średnie miesięczne wartości dostępnych wskaźników mikrobiologicznych i fizykoche- micznych wody pitnej w Krakowie w badanym okresie 2011–2014 spełniają wymogi obowią- zujących norm krajowych oraz europejskich.
Przedmiotem kolejnego artykułu jest zagadnienie jakości sody kalcynowanej i obecnych w niej zanieczyszczeń. Wójcicki badał korelację pomiędzy tymi zanieczyszczeniami a wid- mami sody wykonanymi w bliskiej podczerwieni, stosując do analizy modeli regresji PLS oraz PCR. W pracy stwierdzono, że zaproponowana metoda spektroskopii NIR z wykorzysta- niem omówionych modeli regresji może stanowić nowe obiecujące podejście w zakresie me- todyki oceny jakości wytwarzanej sody kalcynowanej.
W kolejnej pracy Jarossová przedstawia wstępne wyniki badań własnych dotyczące po- staw słowackich konsumentów w odniesieniu do żywności funkcjonalnej. Autorka analizuje wybrane zachowania zakupowe konsumentów względem żywności funkcjonalnej. W pracy stwierdzono, że słowaccy konsumenci kupują żywność funkcjonalną głównie w celu zapobie- gania chorobom ze względów zdrowotnych oraz ze względu na jej smak. Czynnikiem ograni- czającym te zakupy jest według Autorki wyższa cena żywności konwencjonalnej w porówna- niu z cenami produktów tradycyjnych.
Ocena jakości sensorycznej jaj pochodzących z produkcji ekologicznej i konwencjonalnej stanowi przedmiot badań Witt i Śmiechowskiej. Na podstawie badań przeprowadzonych w grupie konsumentów z zastosowaniem pięciopunktowej skali jakości wyróżników jako- ściowych Autorki stwierdzają, że wyższą atrakcyjnością sensoryczną charakteryzują się jaja ekologiczne.
Kawa stanowi jednym z najczęściej spożywanych napojów na świecie. Jednym z charakte- rystycznych składników kawy oprócz związków polifenolowych z grupy kwasów chloroge- nowych jest kofeina. Przedmiotem kolejnej pracy jest ocena zawartości kofeiny w kawach różnych gatunków. Stosując metodę spektrofotometryczną, Dankowska i Kowalski badali zależność pomiędzy sposobem zaparzania kawy a zawartością kofeiny w sporządzonych napa- rach. Stwierdzono, że najwyższą zawartością kofeiny charakteryzują się napary przygotowane sposobem ciśnieniowym niż napary sporządzone sposobem zwykłym.
Kombucha jest nowowoczesnym napojem przygotowywanym na bazie fermentowanej herbaty. Ocena jakości tego napoju stanowi przedmiot badań empirycznych Jakubowskiego i Śmiechowskiej. W pracy przedstawiono wyniki badań własnych autorów dotyczące charak- terystyki fizykochemicznej tego produktu. Wykazano, że kombucha jest naturalnym napojem o niskiej wartości pH, który stanowi bogate źródło przeciwutleniaczy, polifenoli, kwasów orga- nicznych, witaminy C oraz witamin z grupy B. Stwierdzono, że kombucha może być uznana za interesujący produkt charakteryzujący się wysokim potencjałem rynkowym.
Badania jakości wina, a zwłaszcza smaku, wymagają nie tylko wysokiej wrażliwości sen- sorycznej, ale także ogromnego doświadczenia testera. Brodnicka i Szpakowska podjęły próbę sprawdzenia, czy metody instrumentalne pozwolą obiektywne na rozróżnienie smaku czerwo- nych win wytrawnych pochodzących z polskich i francuskich winnic. W tym celu testowano możliwości zastosowania potencjometrycznego sensora smaku z elektrodami typu ASSE.
W pracy stwierdzono, że opisany nowy sensor może być używany do rozróżniania win czer- wonych z polskich i francuskich winnic.
Kolejne dwie prace dotyczą jakości kosmetyków. W pierwszej z nich Malinowska i Kuja- łowicz dokonują analizy oferty rynkowej kosmetyków przeciwzmarszczkowych przeznaczo- nych do pielęgnacji skóry dojrzałej. W pracy oszacowano zakres zastosowania składników ak- tywnych, naturalnych olejów i ekstraktów w produktach przeciwzmarszczkowych oraz po- dział wszystkich analizowanych kosmetyków ze względu na ich przeznaczenie kosmetyczne, grupy wiekowe i zakresy ich cen półkowych.
W drugiej z nich Utracik i Zieliński przedstawiają wyniki badań własnych dotyczące wła- ściwości kremów kosmetycznych zawierających oleje z wiesiołka dwuletniego i czarnuszki siewnej. W pracy omówiono wyniki badań właściwości reologicznych i kosmetycznych otrzymanych kremów. Stwierdzono, że wszystkie badane kremy kosmetyczne wytworzone z dodatkiem stosowanych olejów roślinnych są układami rozrzedzanymi ścinaniem, które wykazują właściwości reologiczne charakterystyczne dla płynów niebinghamowskich. Wyka- zano, że obecność oleju z czarnuszki siewnej w składzie fazy tłuszczowej kremu kosmetycz- nego prowadzi do poprawy takich parametrów sensorycznych jak natłuszczenie, rozprowa- dzalność kremu skórze oraz stopień wygładzenia skóry.
Przedmiotem dwóch ostatnich prac są surfaktanty i ich właściwości. W pierwszej z nich Wieczorek i współautorzy omawiają aktywność przeciwdrobnoustrojową otrzymanych przez tych autorów nowych surfaktantów amfoterycznych należących do sulfobetain. Na podstawie przeprowadzonych badań własnych wykazano, że otrzymane sulfobetainy charakteryzują się wysoką aktywnością antybakteryjną. Stwierdzono, że obserwowana aktywność antybakteryjna zależy nie tylko od długości hydrofobowego łańcucha alkilowego, ale także od struktury czę- ści hydrofilowej cząsteczki surfaktantu.
W drugiej z nich Szutowska i Gwiazdowska poszukują nowych biosurfaktantów wykazu- jących właściwości emulgujące, co może znaleźć zastosowanie do likwidacji skutków rozpry- sku ropy naftowej. Autorki omawiają wyniki własnych badań przesiewowych bakterii kwasu mlekowego, będących potencjalnymi producentami biosurfaktantów. Doświadczalnie wyka- zano, że bakterie fermentacji mlekowej wyizolowane z przewodów pokarmowych zwierząt monogastrycznych są zdolne do syntezowania biosurfaktantów. Stwierdzono, że tak uzyskane
mikrobiologiczne środki powierzchniowo czynne mogą być zastosowane jako alternatywa w stosunku do konwencjonalnych antybiotyków dla świń i drobiu.
Pięćdziesiąty czwarty numer naszego kwartalnika zamyka stała rubryka „Informacje TPJ”.
Zamieszczono w niej informacje o osobach, które w 2017 roku poświęciły część swojego czasu na dokonanie recenzji licznych prac proponowanych do publikacji na łamach naszego czasopisma „Polish Journal of Commodity Science”. W tym miejscu wszystkim naszym Re- cenzentom w imieniu redakcji składam serdeczne słowa podziękowania za ogromny trud wło- żony w przygotowanie recenzji oraz konstruktywne uwagi, co pozwoliło na podniesienie jako- ści publikowanych na naszych łamach artykułów.
Życzę Państwu przyjemnej lektury.
Redaktor TPJ
prof. dr hab. inż. Ryszard Zieliński
According to the long-term plan accepted by the Editorial Board, in the first days of January 2018 we present to our readers the 54th issue of the “Polish Journal of Commodity Science”. Continuing the efforts to widen the group of our readers all the papers are published in English. We would like to remind that now, only papers written in English are accepted by the editors. As before, each paper contains a wide summary in Polish and English. The summaries in both language versions of all the works published one can find on our web page http://www.tpj.uniwersytetradom.pl. Moreover, at the web page an open-access to all the papers published up to 2016 is offered.
A series of 12 papers in the current issue of our journal is opened by two articles on environmental quality. The first work is devoted to technological innovations related to the implementation of the concept of sustainable development. Adamczyk presented the technological innovations in the field of zinc concentrates recycling in industry. The recycling zinc concentrate from wastes in the modified Waelz kiln process was analyzed. Problems of classifying a full-value zinc concentrate obtained in this process are discussed in terms of the provisions of the Waste Act and REACH registration.
In the second work Jachimowski discusses the issue of the quality of drinking water supplied by the water supply network of the city of Krakow. On the basis of the analysis of experimental data it was found that the quality of water depended mainly on the source of its origin. It was shown that the average monthly values of microbiological and physicochemical indicators of drinking water in Kraków in the 2011–2014 period met the requirements of both national and European standards.
The subject of the next article is the issue of the quality of soda ash and its contamination.
Wójcicki studied the correlation between these pollutants and the soda spectra taken in the near infrared using the analysis of PLS and PCR regression models. The study concluded that the proposed method of NIR spectroscopy using the discussed regression models might constitute a new promising approach in the methodology of assessing the quality of soda ash produced.
In the consecutive paper, Jarossová presents the preliminary results of her research on the attitudes of Slovak consumers related to functional foods. The Author analyzes selected consumer purchasing behaviors in relation to functional food. The study states that Slovak consumers buy functional foods mainly for the purpose of disease prevention, for health reasons and because of its taste. The factor limiting these purchases is, according to the author, a higher price of functional food in comparison with the prices of traditional products.
Evaluation of sensory quality of eggs from organic and conventional production is the subject of research by Witt and Śmiechowska. On the basis of research carried out in the group of consumers using a five-point quality scale, the authors distinguish quality ecological eggs with higher sensory appeal.
Coffee is one of the most-consumed beverages in the world. Apart from polyphenolic compounds from the group of chlorogenic acids, the characteristic component of coffee is caffeine. The subject of the next work is the assessment of the caffeine content in coffees of various species. Using the spectrophotometric method, Dankowska and Kowalski investigated the relationship between the method of brewing coffee and the caffeine content in prepared infusions. It was found that in the infusions brewed by pressure method the content of caffeine was higher than in infusions prepared in the usual way.
Kombucha is a modern beverage prepared on the basis of fermented tea. The quality of this drink is the subject of empirical studies by Jakubowski and Śmiechowska. The paper presents the research results on the physicochemical characteristics of this product. Kombucha was shown to be a natural, low-pH drink, which was a rich source of antioxidants, polyphenols,
organic acids, vitamin C and B group vitamins. It was found that kombucha could be considered as an interesting product characterized by high market potential.
Research on the quality of wine, especially its flavor, requires not only a high sensory sensitivity but also a huge tester experience. Brodnicka and Szpakowska attempted to check whether the instrumental methods allowed for an objective distinction of red dry wines from Polish and French vineyards. For this purpose, the possibilities of using a potentiometric flavor sensor with ASSE type electrodes were tested. The study stated that the new sensor described could be used to distinguish between red wines from Polish and French vineyards.
The consecutive two papers concern the quality of cosmetics. In the first one, Malinowska and Kujałowicz analyze the market supply of anti-wrinkle cosmetics designed for mature skin care. The estimation of the scope of application of active ingredients, natural oils and extracts in anti-wrinkle products and the division of all analyzed cosmetics due to their cosmetic use, age groups and ranges of their market prices were presented in the article.
In the second one, Utracik and Zieliński present the results of their research on the properties of cosmetic creams containing evening primrose and sapphire oil. The results of research on rheological and cosmetic properties of the creams were discussed. It was found that all cosmetic creams produced with the addition of used vegetable oils were non- binghamian fluids exhibiting a shear thinning behavior. It was also proved that the presence of black carmine oil in the fat phase of the cosmetic cream led to the improvement of sensory parameters such as lubrication, spreadability over the skin and the degree of skin smoothing.
The subject of the last two works are surfactants and their properties. In the first of these, Wieczorek et al. discuss the antimicrobial activity of the new amphoteric surfactants belonging to the sulfobetain group. On the basis of the tests performed, it was shown that the sulfobetaines obtained were characterized by high antibacterial activity. It was also found that the observed antibacterial activity depended not only on the length of the hydrophobic alkyl chain, but also on the structure of the hydrophilic part of the surfactant molecule.
In the second one, Szutowska and Gwiazdowska are looking for new biosurfactants with emulsifying properties, which can be used to eliminate the effects of oil splashes. The authors discuss the results of their screening tests for lactic acid bacteria, which are potential producers of biosurfactants. It was experimentally demonstrated that lactic acid bacteria isolated from alimentary tracts of monogastric animals were able to synthesize biosurfactants.
Moreover, it was found that the microbiological surfactants obtained in this way could be used as an alternative to conventional antibiotics for pigs and poultry.
The 54th issue of the quarterly is closed by the column „TPJ Announcements”. One can find there information on the scientists who devoted their time to review the numerous papers sent to “Polish Journal of Commodity Science” in 2017. At this point, on behalf of the editorial board, I would like to thank you for the enormous effort put in the preparation of the reviews and constructive comments, which allowed us to improve the quality of the papers published on our pages.
I wish you a nice reading
PJCS Editor
Prof. dr hab. inż. Ryszard Zieliński
Wacław ADAMCZYK Cracow University of Economics
Faculty of Commodity Science and Product Management Chair of Product Technology and Ecology
Technological innovations in recycling of zinc concentrates
Received: October 5, 2017, accepted: October 21, 2017 DOI: 10.19202/j.cs.2018.01.01
Key words: recycling, kiln process, zinc bearing waste.
Słowa kluczowe: recykling, proces przewałowy, odpady cynkono- śne.
1. Introduction
Among industrial branches that pay special attention to the implementation and development of raw materials recycling both in Poland and in the world is the non- ferrous metals industry. Metallurgical processes are a source of harmful emissions into the environment in gaseous, liquid and solid form. Reducing the adverse environmental impact beside of protecting processes used for wastewater reduction and neutralization includes also processes for reducing dust and gas emissions. As a result dusts and sludge are generated, mainly from hydrometallurgical processes, that are collected and deposited or can be recycled to obtain metallic element concentrates being a substitute of the concentrate obtained from ore as a primary raw material.
An example of such designed process is recycling of waste materials from hydrometallurgical processes in the form of zinc bearing sludge and electric arc furnace dusts. Processes of zinc metallurgy are a source of emissions generated during zinc ore processing referred to as zinc primary production. They include in the first place enrichment processes to produce a zinc ore concentrate, and recycling processes to form a zinc
concentrate from waste materials generated in the ore enrichment processes, zinc production from concentrates and dust waste from electric arc furnace processes containing zinc. From a concentrate so obtained metallic zinc can be produced. The final waste stream contains Waelz slag that can also be exploited economically.
2. BAT conclusions inspiring process innovations in zinc metallurgy and waste recycling
The BAT recommendations related to the use of best available techniques being one of the basic prerequisites for achieving sustainable development are important for implementing improvements and developing new technologies. The BAT conclusions define the reference emission levels that should not be exceeded under normal operating conditions when issuing integrated permits for industrial plants. The BAT conclusions are established by the European Commission, while permissible emission levels are defined by administrative bodies of the member states of the EU that issue permits according to the rules of integrated pollution prevention and control [1].
The BAT conclusions referred to the non-ferrous metal industry are contained in the Commission Implementing Decision (EU) 2016/1032 of 13 June 2016 according to the above mentioned directive. (EU Official Journal 30.06.2016). The BAT conclusions refer to some types of activities being performed by
the non-ferrous metal industry, especially to ore roasting and sintering, and ore concentrate processing, non-ferrous metal production from ore, concentrates or secondary materials in the chemical, electrolytic and metallurgical processes. In addition these conclusions refer to non- ferrous metal melting and fusing and foundry operation and product recovery for foundries of capacity of over 20 t per day (4 t for lead and cadmium), as well as energy issues related to the non-ferrous metal industry.
The BAT conclusions recommend to process zinc bearing waste materials to obtain metallic zinc, while maintaining the specified rules and procedure in selection and implementation of recycling processes that are also a source of waste emissions. In this case recycling is justified by significant cumulative emission reduction and also metallic zinc recovery, while reducing the use of ore as a primary raw material. It is easy to see that these activities are reasonable in view of its ecological and economic effects.
The recycling processes referred to as secondary zinc production in the BAT conclusions have been assigned relevant recommendations, when considering that they are a source of complex emissions in the form of:
1) dusts and metals from slag granulation and processing: it is recommended to use bag filters to reduce dust emissions below 5 mg/Nm3,
2) dusts and metals into the atmosphere from melting metallic and metallic/oxide streams, and the slag fuming and Waelz kiln processes: it is recommended to use bag filters to reduce dust emissions 2–5 mg/Nm3 (daily average or average over the sampling period, respectively), if a bag filter is not applicable, the upper limit of emissions can be 15 mg/Nm3;
3) organic compound emissions from the processes mentioned above: it is recommended to introduce a carbon adsorbent and bag filter or electrofilter, or a thermal oxidizer as an alternative;
4) total volatile organic compounds: 2–20 mg/Nm3 (daily average or average over the sampling period, respectively), and PCDD/F: ≤ 0.1 ng I-TEQ/Nm3 from above processes (Total volatile organic compounds – total volatile organic carbon – the sum of all organic compounds sampled on a flame ionization detector and converted into total carbon;
PCDD/F – Polychlorinated dibenzo-p-dioxins and dibenzofurans (1 congeners); I – TEQ – International Toxic Equivalent- Annex VI part 2 of Directive 2010/75/EC) [1]),
5) acid emissions from above processes, in particular HCl and HF into the atmosphere: it is recommended to use an adsorbent and bag filter, and a wet scrubber in the slag fuming process to reach emission of HCl ≤ 1.5 mg/Nm3, HF ≤ 0.3 mg/Nm3(average over the sampling period),
6) emissions from wastewater generation and treatment: reducing the use of fresh water in the Waelz kiln processes by counter-current multistage washing, and implementing crystallisation to reduce halide emissions from these processes.
7) other emissions from the zinc ingot melting, fussing and smelting and zinc powder production, including emissions of organized and dispersed dusts: it is recommended to use bag filter and vacuum equipment, correspondingly, to reach the reference level of zinc dust emissions ≤ 5 mg/Nm3, wastewater emissions: it is recommended to reuse of cooling water, and regarding waste materials it is recommended to utilize local disposal and recycling of residues.
Limitations contained in the BAT conclusions define the reference levels for issuing permits and emission control, but in the first place they inspire technological innovations aimed at significant waste reduction. The recommendations presented under paragraphs 1–7 indicate directions of R&D work targeted at recycling technology.
There are global tendencies in the development of innovations in zinc metallurgy, especially in the raw material and energy management. At first place the work targeted at the
reduction of operating costs and energy consumption, and implementing technical improvements for productivity enhancement is being completed. Due to continuous industrial demand for zinc and the necessity to meet sustainable development guidelines it is necessary to develop recycling processes as indicated by branch analyses presented at the international form in Kyoto in 2005 [2–4]. An example of innovative solutions is the INDUTEC®/EZINEX® hybrid process consisting in treatment of zinc containing secondary materials and metallic zinc production as well as the ZINCEX™ process based on solvent ex- traction [5]. This process has been successfully implemented in the Scorpion Zinc, Namibia [6]. In Poland the work comprising technological innovations in zinc metallurgy is carried out bt the Institute of Non-Ferrous Metals in Gliwice in cooperation with the mining and metallurgical plant ZGH Bolesław S.A.
3. The origin of zinc bearing waste generation and processing improvement in Poland
Currently, in Poland zinc and lead metallurgy concentrates in the Olkusz area, since zinc and lead ore deposits are located here. Zinc-lead ores are mined and processed in the Olkusz and Jaworzno area for many centuries. Initially, this applied primarily to silver and lead ores.
Only in the 19th century an increased interest in zinc compound extraction was observed [7].
The extractable ore deposits are located in the north eastern part of the Upper Silesia Coal Basin referred also to in the literature as the Silesian-Cracow region that is the world's largest zinc and lead ore deposit [8]. Poland is the third-ranked zinc and lead producer in Europe.
The recoverable resources of zinc and lead ores was 93.83 million tonns as of the end of 2015, thus corresponding to 3.5 million tonnes of zinc and 1.42 million tonnes of lead.
A significant increase in demand for zinc at that time resulted from the needs of metallurgy and machine-building industry and building engineering. As a consequence of zinc ore enrichment and zinc production is generation of waste that creates a hazard to the environment due to the presence of heavy metals and metalloids such as Fe, Cd, Ag, Tl, Cu, As, Sb [9].
During the last sixty years zinc and lead ores were mined from deposits located in the Bolesław and Olkusz region.
Deposit extraction, zinc and lead ores are enrichment and final production of these metals and alloys are carried out by ZGH Bolesław S.A. (mine and metallurgical plant). In 2016 the output level reached 2.3 million tonnes of ore from which after initial separation of rock material 50 thousand tonnes of aggregate being a building material were obtained. A gradual depletion of ore deposits in the area of the Pomorzany mine required a new mining concession to be granted to maintain extraction continuation in the Klucze region. Due to the vicinity of ore deposits the extraction required no new surface infrastructure and mining will be possible until the end of 2020. The next applications for mining concession are planned.
In practice the ore processing methods were modified, primarily because of its differentiated composition and gradual ore empoverishment and old deposit depletion and new deposit exploitation. One of the most important modification consists in the implementation of a separate collective process so the the percentage of primary sludge does not exceed 4–5%.
This can be reached by keeping an adequately high share of process returns from the final stages of collective flotation and collective concentration cleaning in respect of primary sludge stream [11].
In the source literature te attention is paid on the development of ore enrichment process consisting in improving separation in the classification process and increasing ore milling efficiency by introducing new modern hydrocyclones, zinc blende flotation modernization by using large sized equipment, the implementation of galena flotation into the milling process for initial separation of 30–40% of total lead in the form of galena concentrate containing
70–75% Pb, implementation of after-floatation waste recycling for zinc and lead concentrates production, and reducing other waste by using its as an aggregate additive [10].
An innovative improvement of the zinc concentrate production process from zinc bearing waste in the Waelz kiln process is a method of build-up reduction in the Waelz kiln.
A massive build-up decreases the kiln cross-section. This reduces the amount of charge being processed and build-up removal causes downtimes of the kiln. The mechanism build-up formation is presented in the description of the invention. In the alkali process where limestone is used as a fluxing agent the build-ups are brittle and easy to remove, while in the acid mode where sand is a flux, hard build-ups and hard to remove are formed. Therefore, the process consisting in maintaining the charge balance alkalinity (Ca+MgO):(SiO2+Fe) up to 0.95. The charge should contain by weight no more than 28% of zinc, 7.5% of lead, 0.8% of cadmium, 7–34% of water, 35–48% of coke breeze compared to the dry matter of a zinc bearing charge. Keeping the charge moisture content up to 34% by weight facilitates loading the kiln. Quartz sand is added to the charge at least at stoichiometric amount to form fayalite (iron silicate). The alkalinity index is changed depending on the composition of charge. The process is carried out in such a way to avoid formation of hard to remove ferruginous build- ups in the reduction and oxidation zone, since originated iron silicate does not undergo reduction at 1250ºC. Originated slag is in the form of fayalite vitrified lumps or clogs, thus preventing heavy metal residues from dissolving or weathering [12].
4. Recycling of zinc bearing raw materials in the Waelz kiln process at ZGH Bolesław
Since for about 60 years no waste generated in ore mining and processing from three mines operating in this region, about 60 million tonnes of waste were collected that at present along with waste materials delivered from metallurgy and other sources are the charge for production of zinc and lead concentrates. Recycling of these metals is cost-effective due to lasting high prices of metals and its concentrates. Current zinc price reaches 2,495 USD/t at the break-even point of around 1,000 USD/t [13].
About 120 thousand tonnes of waste are processed annually at ZGH Bolesław to produce 40 thousand tonnes of zinc and lead concentrate. Recycling of zinc bearing waste materials is carried out in the Waelz kiln process, where zinc bearing waste from zinc hydrometallurgy, metallurgical dusts, etc., coke breeze as a reducing agent, and fluxes in the form of limestone and sand.
The charge is prepared in appropriate proportions and pelleted, continuously fed from the silos (feeding hoppers) with a feed chute into the rotary kiln. In Waelz kilns the feed material is first dried at a temperature of approximately 1100–1250oC, a then counter-current roasting with exhaust gases is carried out. In a reducing atmosphere zinc and heavy metals are initially vaporized, and then oxidized with excess air, cooled and collected as a dust in bag filters.
Depending on the composition of the kiln feed a zinc concentrate is separated from other components, mainly lead.
Zinc concentrate produced from waste recycling in the Waelz kiln process is a solid material (powder or granulate) containing a significant amount of zinc. Zinc content in the concentrate depends on the charge used in the Waelz process. The main component of the charge are waste metallurgical dusts and other zinc bearing waste materials. For waste metallurgical dust processing the zinc content in the concentrate is 50–63%, while for other zinc bearing waste materials the zinc content is 40–55%.
The zinc recovery from the Waelz kiln process is up to 95%. This a wasteless process that meets the BAT requirements. The parameters of environmental impact for zinc recycling at the ZGH Bolesław are presented in Tables 1 and 2.
Table 1. Dust and gas emissions from zinc recycling in the Waelz kiln process Tabela 1. Emisje pyłów i gazów z recyklingu cynku w procesie przewałowym Waelza
Item Emission components Emissions
kg/Mg product kg/year
1 Dusts 0.339 10,000
2 Arsenic 0.00024 7
3 Zinc 0.0097 2882
4 Cadmium 0.0012 37
5 Lead 0.0251 741
6 Sulphur dioxide 3.80 112,000
7 Nitrogen oxides 1.02 30,000
8 Carbon monoxide 13.81 407,000
9 Carbon dioxide 1452 42,802,000
Source/Źródło: [14].
Cooled gases remaining after dust removal before being fed to the discharge point are subject to wet desulphurization and obtained sulphur dioxide is sent to react with CaCO3
suspension forming synthetic gypsum CaSO4·2H2O. The solid residue resulting from roasting in the form of Waelz slag is discharged continuously. After cooling, crushing and screening this slag may be used in road construction, or as a flux in cement production, or as a iron source in metallurgy.
Waelz oxide can be subject to leaching processes with sodium carbonate to remove chlorides, fluorides, sodium, potassium and sulphur so that after drying it can be used as a full- featured feed material in the zinc electrolysis process.
Table 2. Solid waste generated from zinc recycling in the Waelz kiln process
Tabela 2. Odpady stałe powstające przy recyklingu cynku w procesie przewałowym Waelza
Item Waste type kg/Mg product Mg/year
1 Waelz slags 2.689 57,100
2 Refractories and furnace liners cotaining
hazardous substances 0.014 300
Source/Źródło: [14].
5. Problems with classification of zinc concentrate from recycling
Despite of relatively high zinc content in this concentrate, sometimes exceeding the content of this metal in zinc concentrates obtained by flotation methods, some doubts arise concerning classification of a concentrate produced from waste materials. According to the GUS (Central Statistical Office in Poland) this is a processed waste that can be used economically. For comparison, the Bulk collective concentrate originated from zinc and lead ore flotation processing containing 47–51% of zinc.
As defined in the Act on waste: “a waste is any substance or object the holder discards, intends to discard or is required to discard” [15]. In the UE regulations besides of waste materials that are required by law to be removed, an intention related to “discarding” of those substances or materials considered to be useless is indicated [16]. Intentional qualifying included into the mentioned definition is connected with a context determined by further procedure. Thus, such approach allows further procedure to be chosen, in this case consisting in a such targeted waste processing to obtain a product of intended performance, regardless of
the technology used. In addition, the term “discarding” is not adequate for a product, since by definition it is assumed that a product is intended for sale. As subject concentrate is an effect of Waelz technological process that gives it a value-in-use is a full-featured marketable product intended for sale and used as a raw material for zinc production. This complies with the EU Directive on waste, Article 6.1 [16], according to which waste lost its status when were subjected to waste recovery process, including recycling, in particular when: a given substance or object is commonly used for the specific purposes; there is a market for such substances and objects or a need for them; when such substances and objects meet technical specifications for specific purposes and the requirements of applicable regulations and standards; the use of a given substance or object does not lead to general adverse environmental effects.
In the light of this directive the subject concentrate has no the status of waste. It meet iunctim (all together) criteria mentioned in the directive. This is a product required due to its value-in-use and its production process itself has a positive environmental impact. Similar conclusion is drawn from the definition of recycling contained in the Act on waste of 2013 [15] where it is stated that: “recycling means any recovery operation by which waste materials are reprocessed into products, materials or substances whether for the original purpose or other purposes, including material reprocessing but it does not cover energy recovery and reprocessing into materials that can be used as fuels or mine backfilling. Thus, this definition indicates that recycling means a process consisting in waste reprocessing into full-featured products [17]. The Waelz process has been specially designed to produce a zinc concentrate and zinc recovery from secondary materials. The concept of this process is based on the reduction, vaporization and re-oxidation of the feed material to obtain an appropriate zinc oxide concentration. The process meets also the BAT conclusions related to the environmental impact of technological processes. The concentrate produced in this process has been assessed positively for providing safety of marketable chemical substances according to the regulation of the European Chemicals Agency and is a REACH registered substance. This should be emphasized, as the REACH Regulation does not apply to waste materials. Thus the REACH registration confirms “eo ipso” that the subject concentrate fulfils the requirements as a product. The REACH registration is obligatory and its refusal decided by the European Chemical Agency should indicate that the product is excluded from the Community market.
The subject concentrate as an internationally marketed product is subject to the applicable CN 2016 statistical nomenclature according to the Commission Implementing Regulation (EU) 2015/1754 amending Annex I to Council Regulation (EEC) No 2658/87 on the tariff and statistical nomenclature and on the Common Customs Tariff. Since this amendment does not apply to Chapter 26 the subject concentrate is still classified according to this regulation as:
CN 26 08 0000 Zinc ores and concentrates [19]. Moreover, it follows from the mentioned regulations, and due to its chemical composition and production method as well and its in- tended use that the zinc concentrate obtained from waste recycling is a full-featured product that can be identified as: 07.29.15.4 Zinc concentrates according to the Polish Classification of Goods and Services of 4 September 2015 [20].
6. Conclusions
Over the past decade an interest in the implementation of technological innovations targeted at recycling improvement can be seen again. In zinc concentrate recycling under investigation the significance of domestic engineering solutions in the background of worldwide technology development, especially those of conducted by the research teams at the IMNŻ (Institute of Nom-Ferrous Metals) in Gliwice and ZGH Bolesław should be emphasized.
The depletion of zinc bearing resources and the need to gain new concessions on sustain metallurgical production at a high demand for zinc and zinc concentrates and its alloys forcing making full use of raw materials of differentiated composition, especially in regard of zinc, lead, cadmium and iron. Slag produced in the Waelz kiln process is used, besides of many emission reducing uses, has a significant effect on wasteless features of this technology. There are also significant environmental conditions among which the BAT conclusions provide an inspiration for research work. The presented technological innovations enable zinc concentrate to be produced from waste raw materials and to control this process according to the feed material used. The material recycled from the Waelz process meets the REACH criteria and is classified as a full-featured zinc concentrate.
7. Acknowledgment
The project was realized with funds to maintain UEK's research potential.
8. References
[1] Directive 2010/75/UE of the European Parliament and of the Council on industrial emissions.
[2] Umestu Y. (2005) Advances and challenges in zinc production, [in]: Proceedings of International Symposium on Lead and Zinc Processing, Kyoto, October 17–19, 2005, 89–101.
[3] Takashi N. (2005) Zinc recycling technology now and future, [in]: Proceedings of International Symposium on Lead and Zinc Processing, Kyoto, October 17–19, 2005, 123–137.
[4] Yamashita A., Morita E.(2005), Operational Improvements at Annaka Refinery Resulting from Change of Main Ore Source, [in]: Proceedings of International Symposium on Lead and Zinc Processing, Kyoto, October 17–19, 2005, 265–277.
[5] Maccagni M.G. (2016), INDUTEC®/EZINEX® Integrate Process on Secondary Zinc – Bearning Materials. Journal of Sustainable Metallurgy, 2, 133–140.
[6] Moats M.S., Cashwell W.J., Staley A. (2014) A review of the modified zincex® process from skorpion to horsehead, [in]: 2014 SME Annual Meeting and Exhibit, SME 2014:
Leadership in Uncertain Times; Society for Mining, Metallurgy and Exploration, 499–502.
[7] Cabała J., Sutkowska K. (2006) Wpływ dawnej eksploatacji i przeróbki rud Zn – Pb na skład mineralny gleb industrialnych, rejon Olkusza i Jaworzna. Prace Naukowe Instytutu Górnictwa Politechniki Wrocławskiej 117, Studia i Materiały 32, 13–22 (in Polish).
[8] Bonda R. i in. (2016) Bilans zasobów złóż kopalin w Polsce według stanu na 31. XII.
2015. Praca zbiorowa pod red. M. Szutlickiego, A. Malon, M., Tymińskiego, Państwowy Instytut Geologiczny, Warszawa, 54–57 (in Polish).
[9] Cabała J. (2010) Cynk w technosferze. Górnictwo i Geologia, Tom 5, Zeszyt 4, 63–76 (in Polish).
[10] Cichy K., Szołomicki Z., Reguła C. (2007) Nowe technologie w procesie wzbogacania rud Zn-Pb w Zakładach Górniczo-Hutniczych Bolesław S.A. Rudy i Metale Nieżelazne, nr 7, 595–600 (in Polish).
[11] Opis Patentowy PL 186157 B1 (2003) Sposób otrzymywania koncentratów z rudy blen- dowej, zwłaszcza z rudy o zróżnicowanych aktywnościach flotacyjnych jej minerałów i zwiększonym udziale ziarn najdrobniejszych (in Polish).
[12] Opis Patentowy PL 195766 B1 (2007) Sposób otrzymywania koncentratu cynkowego w procesie przewałowym, zwłaszcza z odpadowych materiałów cynkonośnych (in Polish).
[13] Jarosiński A., Madejska L. (2008) Gospodarka Surowcami Mineralnymi, Tom 24, Ze- szyt 4/4, 105–115 (in Polish).
[14] Chmielarz A., Czaplicka M. (2008) Materiały informacyjne do nowelizacji dokumentu referencyjnego BAT w przemyśle metali nieżelaznych, IMNŻ Gliwice, p. 14 (in Polish).
[15] Act on waste, Dz.U. of 2013, item 21, Art. 3.1 pkt 6.
[16] Directive 2008/98/EC of the European Parliament and of the Council on waste.
[17] Adamczyk W. (2016) Opinia dotycząca klasyfikacji koncentratu tlenku cynku wyt- warzanego w procesie przewałowym Waleza przez Bolesław Recycling Sp. z o.o., UEK, Kraków (unpublished paper in Polish).
[18] Regulation EC/1907/2006, Official Journal of the EU of 30 December 2006.
[19] Commission Implementing Regulation/2015/1754, Official Journal of the EU of 30 October 2015. L 285/201.
[20] Regulation of the Council of Ministers of 4 September 2015on the Polish Classification of Goods and Services, Dz.U. of 2015, item 1676.
Summary
The recycling processes become more popular while considering the implementation of sustainable development guidelines. The factors determining the development of recycling technologies include in first place an increase in environmental protection requirements, depletion of primary raw materials, increasing demand for secondary raw materials and related price level. Beside extractive industries the processing industry, especially the fuel and power generating and metallurgical industries play a predominant role in waste generation. Waste materials generated in the metallurgical industry differ in terms of chemical composition and in first place are reach in valuable elements and chemical substances that should be recovered to be reused for economic and ecological reasons.
Technological innovations in metallurgy and recycling of zinc concentrates have been characterized in this paper. Special attention has been paid to inspirational significance of the relevant BAT conclusions. The origin of zinc bearing waste generation and processing in Poland and the development of enrichment techniques based on domestic engineering solutions is described. Recycling of zinc concentrate from waste in the modified Waelz kiln process. The problems related to classification of full-featured zinc concentrate obtained in this process are discussed in the light of the Act on waste, REACH regulation on registration, tariff and statistical nomenclature according to the Community Customs Tariff and Polish Product and Service Classification are discussed.
Wacław ADAMCZYK
Uniwersytet Ekonomiczny w Krakowie, Wydział Towaroznawstwa i Zarządzania Produktem, Katedra Technologii i Ekologii Wyrobów
INNOWACJE TECHNOLOGICZNE W RECYKLINGU KONCENTRATÓW CYNKU
Streszczenie
Procesy recyklingu stają się coraz bardziej popularne, zważywszy na realizację założeń zrównoważonego rozwoju. Do czynników, które determinują rozwój technologii recyklingu, należy przede wszystkim wzrost wymagań w zakresie ochrony środowiska, wyczerpywanie się zasobów surowców pierwotnych, wzrost zapotrzebowania na surowce przetworzone
i związany z tym poziom cen. Obok przemysłu wydobywczego dominującą rolę w generowa- niu odpadów odgrywa przemysł przetwórczy, zwłaszcza paliwowo-energetyczny i metalur- giczny. Odpady generowane w przemyśle metalurgicznym są zróżnicowane pod względem składu, a przede wszystkim bogate w cenne pierwiastki i substancje chemiczne, które powinny być pozyskiwane do ponownego wykorzystania ze względów ekonomicznych i eko- logicznych.
W artykule scharakteryzowano innowacje technologiczne w metalurgii i recyklingu kon- centratów cynku. Zwrócono szczególną uwagę na inspirujące znaczenie konkluzji BAT w tym zakresie. Omówiono historię powstawania i przerobu odpadów cynkonośnych w Polsce i rozwój technik wzbogacania opartych na rodzimej myśli technicznej. Poddano analizie recy- kling koncentratu cynku z odpadów w zmodyfikowanym procesie przewałowym Waelza.
Przeprowadzono dyskusję problemów klasyfikacji uzyskanego w tym procesie pełnowarto- ściowego koncentratu cynku, w świetle przepisów Ustawy o odpadach, rejestracji REACH, nomenklatury taryfowej i statystycznej według Wspólnotowej Taryfy Celnej oraz Polskiej Klasyfikacji Wyrobów i Usług.
prof. dr hab. inż. Wacław ADAMCZYK Cracow University of Economics,
Faculty of Commodity Science and Product Management
Chair of Product Technology and Ecology ul. Rakowicka 27, 31-510 Kraków, Poland e-mail: waclaw.adamczyk@uek.krakow.pl
Artur JACHIMOWSKI Krakow University of Economics
Faculty of Commodity Science and Products Management Chair of Product Technology and Ecology
Evaluation of the quality of water
in the water supply network of the city
of Krakow
Received: November 7, 2017, accepted: November 25, 2017 DOI: 10.19202/j.cs.2018.01.02
Key words: drinking water, water quality, water supply network, laboratory analysis.
Słowa kluczowe: woda pitna, jakość wody, sieć wodociągowa, analiza laboratoryjna.
1. Introduction
In recent years, as a result of intensified control and monitoring conducted by sanitary supervision agencies, the quality of the water supplied via distribution networks has considerably improved. Its level is affected by the following factors: the quality of the feed water, the manner of its treatment, the corrosive properties of the water as well as susceptibility to precipitate formation, the sanitary condition of the equipment and the tanks where the water is stored and of the whole water supply network. Furthermore, water should fulfil not only the qualitative but also the quantitative requirements. In this respect, it is necessary to take into account the time water stays in the system as well as the pressure changes in the supply network [1–3].
Water is safe for consumption when the concentration of the additives it contains does not exceed the values that
are permissible with regard to the health and taste considerations. It is the main objective of the treatment processes to obtain water with such properties. It is also of essential importance that the water fed into the distribution network should not change its quality in the course of flowing to the user. In order for this condition to be fulfilled, it must be stable chemically and biologically, and the condition of the water supply network must not cause its contamination [1, 3].
In many countries of the world, the basis for developing standards specifying the quality of drinking water are the guidelines of the World Health Organisation (WHO), which are updated every few years [4]. In Poland, the legal regulations concerning the qualitative requirements are specified in annexes to the Regulation of the Minister of Health of 13th November 2015 on the quality of water intended for human consumption [5]. The aforementioned legal acts were issued based on the Act of 7th June 2001 [6]. And the rules concerning the quality of water intended for human consumption that are in force in member states of the European Union are set forth in the Council Directive 98/83/EC of 3rd November 1998 [7].
The above mentioned Act defines water intended for human consumption as, water intended for drinking, preparing food or for other purposes in households as well as any water utilised for the production of foods, pharmaceuticals and cosmetics, and also for the needs of swimming pools [6].
According to the Regulation of the Minister of Health of 13th November 2015, water is safe for human health if it is free from pathogenic microorganisms and parasites in a number that may pose a hazard to human health, any substances in concentrations that may pose a hazard to human health, and does not have any aggressive corrosive properties [5].
The objective of the study was to evaluate the quality of the mains water that is supplied to consumers from four water treatment plants of the Municipal Water and Sewerage Company (MPWiK S.A.) in Krakow, which – with the exception of one deep-water catchment site – use surface waters as the source of drinking water. The laboratory analysis conducted in the years 2011–2014 concerned selected microbiological and physicochemical parameters determined at selected points of the water supply network.
2. Characteristics of the study area
At present, drinking water for the urban agglomeration is produced at four plants: Raba, Rudawa, Dłubnia and Bielany, which employ a very advanced treatment technology [8]. The Krakow-based water treatment plants take 97% of surface water from the following sources:
the Dobczyce reservoir and the rivers Rudawa, Dłubna and Sanka. Based on the 2015 report from the Krakow treatment plants, it follows that the maximum production capacity of all
Fig. 1. Division of Krakow into operating regions and areas for network and hydrant maintenance Rys. 1. Podział Krakowa na rejony eksploatacyjne i obszary przeglądów sieci i hydrantów
Source: GIS MPWiK S.A. Krakow 2012, after [13].
of the plants was 292,200 m3 water per day. In the year concerned, 57 m3 was pumped into the water supply system, which is a smaller quantity of water produced in comparison with previous years. According to the data of as the end of 2015, the MPWiK S.A. in Krakow operates 2,167 km of water supply network the including the terminals, which means an increase by 33 km compared with the previous year [9, 10]. This network is characterised by a high level of reliability in delivering water to consumers [11, 12]. This is impacted by its structure, which is mostly in a ring arrangement. The city was divided into three main operating regions within the water supply network (Fig. 1) [13, 14]:
The Centrum region, C (15 areas), which serves the districts of Śródmieście (Centre) and Krowodrza;
The Nowa Huta region, H (19 areas), which comprises the network in the area of Nowa Huta;
The Podgórze region, P (17 areas), serving the network in the area of Podgórze;
where the individual regions account for 36.1%, 21.97% and 41.93% of the total length of the network, respectively [15].
At present, the Krakow water supply system (KSZW) comprises forty-six water supply tanks with a total capacity of 309,000 m3, 3 pumping stations and 21 hydrophore pump systems [9].
3. Study methodology
The object of the study was to provide a statistical analysis of the results of laboratory tests of water in the Krakow distribution network. Determinations of the microbiological and physicochemical indicators used in the analysis were carried out in 2011–2014. Samples for the laboratory tests were collected at the given points within the network on average every quarter during each year (Fig. 2). Based on the results obtained, average values were calculated for the four-year study period. The results of the determinations were made available by the Central Laboratory of the MPWiK S.A. in Krakow [16], and the determinations of the selected indicators were made according to the register of research methods [17].
a) b)
c) d)
Fig. 2. Feed water catchment sites for water produced by the Krakow water treatment plants (ZUWs); zones:
a) Rudawa, b) Raba, c) Dłubna, d) Bielany
Rys. 2. Punkty poboru wody wyprodukowanej przez krakowskie ZUW; obszary: a) Rudawa, b) Raba, c) Dłubna, d) Bielany
Source: own study/Źródło: badania własne.
The following statistical parameters: arithmetic mean, standard deviation and coefficient of variability (Cv) expressed as the radio of standard deviation to the mean were computed with a spreadsheet. The Person linear correlation coefficient at significance level p ≤0.05 was determined the strength of correlation between water physicochemical parameters.
By using the SPSS Statistics software the normality of distribution for water quality indicators was analyzed with Shapiro-Wilk and Kolmogorov–Smirnov tests. Since most of measured features showed a distribution that differ from normal, thus to check significance of differences between means of drinking water quality indicators – nonparametric Kruskal- Walis test was used at signifycance level α = 0.05.
Samples of treated water for laboratory tests were collected at a number of points within the distribution network located in different districts of Krakow. These were mostly public facilities, such as schools, kindergartens, shops, petrol stations, administrative offices [18].
In order to make a correct evaluation of the quality of water, it is necessary to learn the values of all of the physicochemical and bacteriological indicators. Samples are analysed over a length of time that allows determination of the greatest possible range of variability in the water composition.
For the selected quality parameters of the mains water, the basic statistical parameters were calculated: the mean, minimum and maximum values, the standard deviation as well as the coefficient of variation.
In 2013, water used for organoleptic examination came from the following points in the city network: ul. Zarzecze 106, ul. Tokarskiego 1, ul. Brożka 3, ul. Kosiarzy 1, ul. Dymarek, os. Górali 5, Kamedulska 70, Mirowska 278 (Tab. 8). Additionally, water was collected from os. Tysiąclecia, ul. Dworna, ul. Kolna, ul. Floriańska and ul. Wróblewskiego. In sensory examinations of the water, the samples analysed had been collected at the 4 Krakow treatment plants and at sampling points in the networks corresponding to the respective plants. For comparative determinations, spring water of the brand Żywiec Zdrój was used. evaluations were performed in May and November 2013.
4. Results and discussion
This chapter presents the detailed statistical analyses that were performed for the selected quality indicators of the mains water. The data that were gathered over the four years of the study comprised parameters of the quality of water collected from the distribution network in the period from 1st January 2011 and 31st December 2014. The analysis took into consideration zones supplying the city with water produced at the four Krakow ZUWs. The selection of 29 sampling points within the entire area of supply made it possible to analyse the water quality in both the operational and the technological aspects.
4.1. Microbiological indicators
In the water collected from the supply network, 5 microbiological indicators were examined: the total number of coliforms, Escherichia coli, enterococci (faecal streptococci), Clostridium perfringens as well as the total number of microorganisms at 22°C after 72 h.
In none of the 100 ml samples of water from the points concerned, bacterial colonies of coliforms, Escherichia coli, enterococci or Clostridium perfringens were detected. And the highest value of the total number of microorganisms at 22°C after 72 h (370 cfu/100 ml) was observed in the water sampled at ul. Kutrzeby 4, in which the mean was 31 cfu/100 ml (Cv = 294%). The lowest values were found in the water supplied from the ZUW Rudawa where means for the analysed points ranged between 1 cfu/100 (Cv = 223%) – ul. Stawowa 179 and 14 cfu/100 ml (Cv = 226%) – ul. Tokarskiego 1. Results of the microbiological ana- lysis of the network water have been presented in Figure 3.
a) b)
c) d)
Fig. 3. Mean values of the total number of microorganisms at 22˚C after 72 h in the tap water of Krakow in 2011–2014; zones: a) Rudawa, b) Raba, c) Dłubna, d) Bielany
Source: own study based on results obtained from the MPWiK.
Rys. 3. Średnie wartości ogólnej liczby mikroorganizmów w 22˚C po 72 h w wodzie wodociągowej Krakowa w latach 2011–2014; obszary: a) Rudawa, b) Raba, c) Dłubna, d) Bielany
Źródło: badania własne na podstawie danych otrzymanych z MPWiK.
4.2. Physicochemical indicators
The physicochemical examination utilised 10 selected quality indicators determined in the water samples collected from the distribution network. The analysis of results from the four- year period is presented below.
The greatest values of the colour parameter were observed in the water supplied from the ZUW Bielany. The average results varied here between 2.46±1.13 mgPt∙dm-3 (ul. Astro- nautów 5) and 7.07±4.57 mgPt∙dm-3, and the maximum value of this indicator was determined at ul. Mirowska 278 (16 mgPt∙dm-3). The lowest values were recorded in the water from the ZUW Raba where the average results ranged between 1.81±0.83 mgPt∙dm-3 (ul. Babińskiego 29) and 3.13±3.00 mgPt∙ dm-3 (ul. Cechowa 57).
