Kamilla Hansen fremlagde resultater fra forsøg lavet på DTU Miljø. Effekten af pH i badevandet på dannelsen af desinfektionsbiprodukter var undersøgt for klorering af kropsvæske analog og partikler opsamlet på tromlefilter. Ved at sænke pH fra 7,5 til 6,5 blev der observeret en reduceret trihalometan dannelsen i begge tilfælde, mens haloacetonitril og trikloramin dannelsen steg. Haloeddikesyrerne var uændret ved klorering af kropsvæske analog og faldt ved partikelforsøget med pH.
For at evaluere betydningen af ændringerne i dannelse af de analyserede biprodukter var den samlede toksicitet beregnet: Toksiciteten blev næsten fordoblet ved pH 6,5 i forhold til pH 7,5 og tredoblet ved pH 6,0. Konklusionerne var at det er tvivlsomt om man får en bedre badevandskvalitet ved at sænke pH selvom THM koncentrationerne falder. Undersøgelsen viser dermed at THM ikke er egnet som testparameter ved evaluering af ændringer i drift af svømmebade eller i vandbehandlingen.
PowerPoint Presentation (currently without audio) about the CFA ~ Cash Flow Analyzer program written for the Hp-12C Calculator and the investmentreal estate market.
Kamilla Hansen fremlagde resultater fra forsøg lavet på DTU Miljø. Effekten af pH i badevandet på dannelsen af desinfektionsbiprodukter var undersøgt for klorering af kropsvæske analog og partikler opsamlet på tromlefilter. Ved at sænke pH fra 7,5 til 6,5 blev der observeret en reduceret trihalometan dannelsen i begge tilfælde, mens haloacetonitril og trikloramin dannelsen steg. Haloeddikesyrerne var uændret ved klorering af kropsvæske analog og faldt ved partikelforsøget med pH.
For at evaluere betydningen af ændringerne i dannelse af de analyserede biprodukter var den samlede toksicitet beregnet: Toksiciteten blev næsten fordoblet ved pH 6,5 i forhold til pH 7,5 og tredoblet ved pH 6,0. Konklusionerne var at det er tvivlsomt om man får en bedre badevandskvalitet ved at sænke pH selvom THM koncentrationerne falder. Undersøgelsen viser dermed at THM ikke er egnet som testparameter ved evaluering af ændringer i drift af svømmebade eller i vandbehandlingen.
PowerPoint Presentation (currently without audio) about the CFA ~ Cash Flow Analyzer program written for the Hp-12C Calculator and the investmentreal estate market.
2024 State of Marketing Report – by HubspotMarius Sescu
https://www.hubspot.com/state-of-marketing
· Scaling relationships and proving ROI
· Social media is the place for search, sales, and service
· Authentic influencer partnerships fuel brand growth
· The strongest connections happen via call, click, chat, and camera.
· Time saved with AI leads to more creative work
· Seeking: A single source of truth
· TLDR; Get on social, try AI, and align your systems.
· More human marketing, powered by robots
ChatGPT is a revolutionary addition to the world since its introduction in 2022. A big shift in the sector of information gathering and processing happened because of this chatbot. What is the story of ChatGPT? How is the bot responding to prompts and generating contents? Swipe through these slides prepared by Expeed Software, a web development company regarding the development and technical intricacies of ChatGPT!
Product Design Trends in 2024 | Teenage EngineeringsPixeldarts
The realm of product design is a constantly changing environment where technology and style intersect. Every year introduces fresh challenges and exciting trends that mold the future of this captivating art form. In this piece, we delve into the significant trends set to influence the look and functionality of product design in the year 2024.
How Race, Age and Gender Shape Attitudes Towards Mental HealthThinkNow
Mental health has been in the news quite a bit lately. Dozens of U.S. states are currently suing Meta for contributing to the youth mental health crisis by inserting addictive features into their products, while the U.S. Surgeon General is touring the nation to bring awareness to the growing epidemic of loneliness and isolation. The country has endured periods of low national morale, such as in the 1970s when high inflation and the energy crisis worsened public sentiment following the Vietnam War. The current mood, however, feels different. Gallup recently reported that national mental health is at an all-time low, with few bright spots to lift spirits.
To better understand how Americans are feeling and their attitudes towards mental health in general, ThinkNow conducted a nationally representative quantitative survey of 1,500 respondents and found some interesting differences among ethnic, age and gender groups.
Technology
For example, 52% agree that technology and social media have a negative impact on mental health, but when broken out by race, 61% of Whites felt technology had a negative effect, and only 48% of Hispanics thought it did.
While technology has helped us keep in touch with friends and family in faraway places, it appears to have degraded our ability to connect in person. Staying connected online is a double-edged sword since the same news feed that brings us pictures of the grandkids and fluffy kittens also feeds us news about the wars in Israel and Ukraine, the dysfunction in Washington, the latest mass shooting and the climate crisis.
Hispanics may have a built-in defense against the isolation technology breeds, owing to their large, multigenerational households, strong social support systems, and tendency to use social media to stay connected with relatives abroad.
Age and Gender
When asked how individuals rate their mental health, men rate it higher than women by 11 percentage points, and Baby Boomers rank it highest at 83%, saying it’s good or excellent vs. 57% of Gen Z saying the same.
Gen Z spends the most amount of time on social media, so the notion that social media negatively affects mental health appears to be correlated. Unfortunately, Gen Z is also the generation that’s least comfortable discussing mental health concerns with healthcare professionals. Only 40% of them state they’re comfortable discussing their issues with a professional compared to 60% of Millennials and 65% of Boomers.
Race Affects Attitudes
As seen in previous research conducted by ThinkNow, Asian Americans lag other groups when it comes to awareness of mental health issues. Twenty-four percent of Asian Americans believe that having a mental health issue is a sign of weakness compared to the 16% average for all groups. Asians are also considerably less likely to be aware of mental health services in their communities (42% vs. 55%) and most likely to seek out information on social media (51% vs. 35%).
AI Trends in Creative Operations 2024 by Artwork Flow.pdfmarketingartwork
This article is all about what AI trends will emerge in the field of creative operations in 2024. All the marketers and brand builders should be aware of these trends for their further use and save themselves some time!
A report by thenetworkone and Kurio.
The contributing experts and agencies are (in an alphabetical order): Sylwia Rytel, Social Media Supervisor, 180heartbeats + JUNG v MATT (PL), Sharlene Jenner, Vice President - Director of Engagement Strategy, Abelson Taylor (USA), Alex Casanovas, Digital Director, Atrevia (ES), Dora Beilin, Senior Social Strategist, Barrett Hoffher (USA), Min Seo, Campaign Director, Brand New Agency (KR), Deshé M. Gully, Associate Strategist, Day One Agency (USA), Francesca Trevisan, Strategist, Different (IT), Trevor Crossman, CX and Digital Transformation Director; Olivia Hussey, Strategic Planner; Simi Srinarula, Social Media Manager, The Hallway (AUS), James Hebbert, Managing Director, Hylink (CN / UK), Mundy Álvarez, Planning Director; Pedro Rojas, Social Media Manager; Pancho González, CCO, Inbrax (CH), Oana Oprea, Head of Digital Planning, Jam Session Agency (RO), Amy Bottrill, Social Account Director, Launch (UK), Gaby Arriaga, Founder, Leonardo1452 (MX), Shantesh S Row, Creative Director, Liwa (UAE), Rajesh Mehta, Chief Strategy Officer; Dhruv Gaur, Digital Planning Lead; Leonie Mergulhao, Account Supervisor - Social Media & PR, Medulla (IN), Aurelija Plioplytė, Head of Digital & Social, Not Perfect (LI), Daiana Khaidargaliyeva, Account Manager, Osaka Labs (UK / USA), Stefanie Söhnchen, Vice President Digital, PIABO Communications (DE), Elisabeth Winiartati, Managing Consultant, Head of Global Integrated Communications; Lydia Aprina, Account Manager, Integrated Marketing and Communications; Nita Prabowo, Account Manager, Integrated Marketing and Communications; Okhi, Web Developer, PNTR Group (ID), Kei Obusan, Insights Director; Daffi Ranandi, Insights Manager, Radarr (SG), Gautam Reghunath, Co-founder & CEO, Talented (IN), Donagh Humphreys, Head of Social and Digital Innovation, THINKHOUSE (IRE), Sarah Yim, Strategy Director, Zulu Alpha Kilo (CA).
Trends In Paid Search: Navigating The Digital Landscape In 2024Search Engine Journal
The search marketing landscape is evolving rapidly with new technologies, and professionals, like you, rely on innovative paid search strategies to meet changing demands.
It’s important that you’re ready to implement new strategies in 2024.
Check this out and learn the top trends in paid search advertising that are expected to gain traction, so you can drive higher ROI more efficiently in 2024.
You’ll learn:
- The latest trends in AI and automation, and what this means for an evolving paid search ecosystem.
- New developments in privacy and data regulation.
- Emerging ad formats that are expected to make an impact next year.
Watch Sreekant Lanka from iQuanti and Irina Klein from OneMain Financial as they dive into the future of paid search and explore the trends, strategies, and technologies that will shape the search marketing landscape.
If you’re looking to assess your paid search strategy and design an industry-aligned plan for 2024, then this webinar is for you.
5 Public speaking tips from TED - Visualized summarySpeakerHub
From their humble beginnings in 1984, TED has grown into the world’s most powerful amplifier for speakers and thought-leaders to share their ideas. They have over 2,400 filmed talks (not including the 30,000+ TEDx videos) freely available online, and have hosted over 17,500 events around the world.
With over one billion views in a year, it’s no wonder that so many speakers are looking to TED for ideas on how to share their message more effectively.
The article “5 Public-Speaking Tips TED Gives Its Speakers”, by Carmine Gallo for Forbes, gives speakers five practical ways to connect with their audience, and effectively share their ideas on stage.
Whether you are gearing up to get on a TED stage yourself, or just want to master the skills that so many of their speakers possess, these tips and quotes from Chris Anderson, the TED Talks Curator, will encourage you to make the most impactful impression on your audience.
See the full article and more summaries like this on SpeakerHub here: https://speakerhub.com/blog/5-presentation-tips-ted-gives-its-speakers
See the original article on Forbes here:
http://www.forbes.com/forbes/welcome/?toURL=http://www.forbes.com/sites/carminegallo/2016/05/06/5-public-speaking-tips-ted-gives-its-speakers/&refURL=&referrer=#5c07a8221d9b
ChatGPT and the Future of Work - Clark Boyd Clark Boyd
Everyone is in agreement that ChatGPT (and other generative AI tools) will shape the future of work. Yet there is little consensus on exactly how, when, and to what extent this technology will change our world.
Businesses that extract maximum value from ChatGPT will use it as a collaborative tool for everything from brainstorming to technical maintenance.
For individuals, now is the time to pinpoint the skills the future professional will need to thrive in the AI age.
Check out this presentation to understand what ChatGPT is, how it will shape the future of work, and how you can prepare to take advantage.
A brief introduction to DataScience with explaining of the concepts, algorithms, machine learning, supervised and unsupervised learning, clustering, statistics, data preprocessing, real-world applications etc.
It's part of a Data Science Corner Campaign where I will be discussing the fundamentals of DataScience, AIML, Statistics etc.
Time Management & Productivity - Best PracticesVit Horky
Here's my presentation on by proven best practices how to manage your work time effectively and how to improve your productivity. It includes practical tips and how to use tools such as Slack, Google Apps, Hubspot, Google Calendar, Gmail and others.
The six step guide to practical project managementMindGenius
The six step guide to practical project management
If you think managing projects is too difficult, think again.
We’ve stripped back project management processes to the
basics – to make it quicker and easier, without sacrificing
the vital ingredients for success.
“If you’re looking for some real-world guidance, then The Six Step Guide to Practical Project Management will help.”
Dr Andrew Makar, Tactical Project Management
2024 State of Marketing Report – by HubspotMarius Sescu
https://www.hubspot.com/state-of-marketing
· Scaling relationships and proving ROI
· Social media is the place for search, sales, and service
· Authentic influencer partnerships fuel brand growth
· The strongest connections happen via call, click, chat, and camera.
· Time saved with AI leads to more creative work
· Seeking: A single source of truth
· TLDR; Get on social, try AI, and align your systems.
· More human marketing, powered by robots
ChatGPT is a revolutionary addition to the world since its introduction in 2022. A big shift in the sector of information gathering and processing happened because of this chatbot. What is the story of ChatGPT? How is the bot responding to prompts and generating contents? Swipe through these slides prepared by Expeed Software, a web development company regarding the development and technical intricacies of ChatGPT!
Product Design Trends in 2024 | Teenage EngineeringsPixeldarts
The realm of product design is a constantly changing environment where technology and style intersect. Every year introduces fresh challenges and exciting trends that mold the future of this captivating art form. In this piece, we delve into the significant trends set to influence the look and functionality of product design in the year 2024.
How Race, Age and Gender Shape Attitudes Towards Mental HealthThinkNow
Mental health has been in the news quite a bit lately. Dozens of U.S. states are currently suing Meta for contributing to the youth mental health crisis by inserting addictive features into their products, while the U.S. Surgeon General is touring the nation to bring awareness to the growing epidemic of loneliness and isolation. The country has endured periods of low national morale, such as in the 1970s when high inflation and the energy crisis worsened public sentiment following the Vietnam War. The current mood, however, feels different. Gallup recently reported that national mental health is at an all-time low, with few bright spots to lift spirits.
To better understand how Americans are feeling and their attitudes towards mental health in general, ThinkNow conducted a nationally representative quantitative survey of 1,500 respondents and found some interesting differences among ethnic, age and gender groups.
Technology
For example, 52% agree that technology and social media have a negative impact on mental health, but when broken out by race, 61% of Whites felt technology had a negative effect, and only 48% of Hispanics thought it did.
While technology has helped us keep in touch with friends and family in faraway places, it appears to have degraded our ability to connect in person. Staying connected online is a double-edged sword since the same news feed that brings us pictures of the grandkids and fluffy kittens also feeds us news about the wars in Israel and Ukraine, the dysfunction in Washington, the latest mass shooting and the climate crisis.
Hispanics may have a built-in defense against the isolation technology breeds, owing to their large, multigenerational households, strong social support systems, and tendency to use social media to stay connected with relatives abroad.
Age and Gender
When asked how individuals rate their mental health, men rate it higher than women by 11 percentage points, and Baby Boomers rank it highest at 83%, saying it’s good or excellent vs. 57% of Gen Z saying the same.
Gen Z spends the most amount of time on social media, so the notion that social media negatively affects mental health appears to be correlated. Unfortunately, Gen Z is also the generation that’s least comfortable discussing mental health concerns with healthcare professionals. Only 40% of them state they’re comfortable discussing their issues with a professional compared to 60% of Millennials and 65% of Boomers.
Race Affects Attitudes
As seen in previous research conducted by ThinkNow, Asian Americans lag other groups when it comes to awareness of mental health issues. Twenty-four percent of Asian Americans believe that having a mental health issue is a sign of weakness compared to the 16% average for all groups. Asians are also considerably less likely to be aware of mental health services in their communities (42% vs. 55%) and most likely to seek out information on social media (51% vs. 35%).
AI Trends in Creative Operations 2024 by Artwork Flow.pdfmarketingartwork
This article is all about what AI trends will emerge in the field of creative operations in 2024. All the marketers and brand builders should be aware of these trends for their further use and save themselves some time!
A report by thenetworkone and Kurio.
The contributing experts and agencies are (in an alphabetical order): Sylwia Rytel, Social Media Supervisor, 180heartbeats + JUNG v MATT (PL), Sharlene Jenner, Vice President - Director of Engagement Strategy, Abelson Taylor (USA), Alex Casanovas, Digital Director, Atrevia (ES), Dora Beilin, Senior Social Strategist, Barrett Hoffher (USA), Min Seo, Campaign Director, Brand New Agency (KR), Deshé M. Gully, Associate Strategist, Day One Agency (USA), Francesca Trevisan, Strategist, Different (IT), Trevor Crossman, CX and Digital Transformation Director; Olivia Hussey, Strategic Planner; Simi Srinarula, Social Media Manager, The Hallway (AUS), James Hebbert, Managing Director, Hylink (CN / UK), Mundy Álvarez, Planning Director; Pedro Rojas, Social Media Manager; Pancho González, CCO, Inbrax (CH), Oana Oprea, Head of Digital Planning, Jam Session Agency (RO), Amy Bottrill, Social Account Director, Launch (UK), Gaby Arriaga, Founder, Leonardo1452 (MX), Shantesh S Row, Creative Director, Liwa (UAE), Rajesh Mehta, Chief Strategy Officer; Dhruv Gaur, Digital Planning Lead; Leonie Mergulhao, Account Supervisor - Social Media & PR, Medulla (IN), Aurelija Plioplytė, Head of Digital & Social, Not Perfect (LI), Daiana Khaidargaliyeva, Account Manager, Osaka Labs (UK / USA), Stefanie Söhnchen, Vice President Digital, PIABO Communications (DE), Elisabeth Winiartati, Managing Consultant, Head of Global Integrated Communications; Lydia Aprina, Account Manager, Integrated Marketing and Communications; Nita Prabowo, Account Manager, Integrated Marketing and Communications; Okhi, Web Developer, PNTR Group (ID), Kei Obusan, Insights Director; Daffi Ranandi, Insights Manager, Radarr (SG), Gautam Reghunath, Co-founder & CEO, Talented (IN), Donagh Humphreys, Head of Social and Digital Innovation, THINKHOUSE (IRE), Sarah Yim, Strategy Director, Zulu Alpha Kilo (CA).
Trends In Paid Search: Navigating The Digital Landscape In 2024Search Engine Journal
The search marketing landscape is evolving rapidly with new technologies, and professionals, like you, rely on innovative paid search strategies to meet changing demands.
It’s important that you’re ready to implement new strategies in 2024.
Check this out and learn the top trends in paid search advertising that are expected to gain traction, so you can drive higher ROI more efficiently in 2024.
You’ll learn:
- The latest trends in AI and automation, and what this means for an evolving paid search ecosystem.
- New developments in privacy and data regulation.
- Emerging ad formats that are expected to make an impact next year.
Watch Sreekant Lanka from iQuanti and Irina Klein from OneMain Financial as they dive into the future of paid search and explore the trends, strategies, and technologies that will shape the search marketing landscape.
If you’re looking to assess your paid search strategy and design an industry-aligned plan for 2024, then this webinar is for you.
5 Public speaking tips from TED - Visualized summarySpeakerHub
From their humble beginnings in 1984, TED has grown into the world’s most powerful amplifier for speakers and thought-leaders to share their ideas. They have over 2,400 filmed talks (not including the 30,000+ TEDx videos) freely available online, and have hosted over 17,500 events around the world.
With over one billion views in a year, it’s no wonder that so many speakers are looking to TED for ideas on how to share their message more effectively.
The article “5 Public-Speaking Tips TED Gives Its Speakers”, by Carmine Gallo for Forbes, gives speakers five practical ways to connect with their audience, and effectively share their ideas on stage.
Whether you are gearing up to get on a TED stage yourself, or just want to master the skills that so many of their speakers possess, these tips and quotes from Chris Anderson, the TED Talks Curator, will encourage you to make the most impactful impression on your audience.
See the full article and more summaries like this on SpeakerHub here: https://speakerhub.com/blog/5-presentation-tips-ted-gives-its-speakers
See the original article on Forbes here:
http://www.forbes.com/forbes/welcome/?toURL=http://www.forbes.com/sites/carminegallo/2016/05/06/5-public-speaking-tips-ted-gives-its-speakers/&refURL=&referrer=#5c07a8221d9b
ChatGPT and the Future of Work - Clark Boyd Clark Boyd
Everyone is in agreement that ChatGPT (and other generative AI tools) will shape the future of work. Yet there is little consensus on exactly how, when, and to what extent this technology will change our world.
Businesses that extract maximum value from ChatGPT will use it as a collaborative tool for everything from brainstorming to technical maintenance.
For individuals, now is the time to pinpoint the skills the future professional will need to thrive in the AI age.
Check out this presentation to understand what ChatGPT is, how it will shape the future of work, and how you can prepare to take advantage.
A brief introduction to DataScience with explaining of the concepts, algorithms, machine learning, supervised and unsupervised learning, clustering, statistics, data preprocessing, real-world applications etc.
It's part of a Data Science Corner Campaign where I will be discussing the fundamentals of DataScience, AIML, Statistics etc.
Time Management & Productivity - Best PracticesVit Horky
Here's my presentation on by proven best practices how to manage your work time effectively and how to improve your productivity. It includes practical tips and how to use tools such as Slack, Google Apps, Hubspot, Google Calendar, Gmail and others.
The six step guide to practical project managementMindGenius
The six step guide to practical project management
If you think managing projects is too difficult, think again.
We’ve stripped back project management processes to the
basics – to make it quicker and easier, without sacrificing
the vital ingredients for success.
“If you’re looking for some real-world guidance, then The Six Step Guide to Practical Project Management will help.”
Dr Andrew Makar, Tactical Project Management
Beginners Guide to TikTok for Search - Rachel Pearson - We are Tilt __ Bright...
PhD thesis defence
1. Forurening af vandmiljøet med steroidøstrogener Henrik Andersen Adjunkt Institut for Analytisk Kemi Danmarks Farmaceutiske Universitet [email_address]
12. Xeno-østrogener fra Nova-programmet 1,32 μg/l 0,5 μg/l BPA <LOQ <LOQ OP 0,68 μg/l 0,4 μg/l NP NOVA 2001 4 μg/l <LOQ BPA <LOQ <LOQ OP 0,29 μg/l <LOQ NP Århus amt Max Median Østrogen
17. Oprindelig vandmetode Forsur til pH = 3,0 & GF/C filtrer 1,00 kg prøve Tilsæt intern standard (E2-acetat) 1 g silika gel (1.5 % H 2 O deaktiveret) Elueres med 5 ml n-hexane/acetone (65/35) Ekstraktion med C18 SPE Derivation med MSTFA, TMSI, DTE. 1 h ved 60 °C. Tilsæt apparat standard (Mirex) GC/ion trap-MS/MS
19. Metoder til slam og spildevand Ternes et al. (2002) Anal. Chem. 74, 3498-3504. Andersen et al., (2003) Env. Sci. Tech. Forsur til pH = 3,0 & GF/C filtrer 1,00 l prøve Tilsæt intern standard (E2-acetat) GPC oprensning cyclohexane/acetone (3:1) Ekstraktion med C18 SPE Derivation med MSTFA, TMSI, DTE. 1 h ved 60 °C. Tilsæt apparat standard (Mirex) 1 g silika gel (1.5 % H2O deaktiveret) Elueres med 5 ml n-hexane/acetone (65/35) GC/ion trap-MS/MS Afvej 0,50 g slam (Aktivt eller endeligt slam) Tilsæt intern standard (E2-Acetat) GPC oprensning cyclohexane/acetone (3:1) Ekstraher 2xmetanol + 2xacetone med ultralyd Derivation med MSTFA, TMSI, DTE. 1 h ved 60 °C. Tilsæt apparat standard (Mirex) 1 g silika gel (1.5 % H2O deaktiveret) Elueres med 5 ml n-hexane/acetone (65/35) GC/ion trap-MS/MS
28. Diagram af renseanlæg Andersen et al., (2003) Env. Sci. Tech. biofosfat denitrifikation gitter sandfilter primær sedimentation nitrifikation FeCl 3 24 h flow proportional prøve grab prøve tromlefilter primært slam overskud af aktivt slam biogas anaerob rådnetank pressefilter endeligt slam 9.350 m 3 11.950 m 3 41.900 m 3 sekundær sedimentation
37. Slam og vand massestrøm i renseanlæg NO 3 - Primær sedimentering Aktivt slamanlæg Sekundær sedimentering Slambehandling Overskudsslam Stof fra primær sedimentering Indløb Udløb Stabiliseret slam Returslam
Editor's Notes
Jeg hedder Henrik Andersen og jeg har været indskrevet som PhD-studerne ved Institut for Analytisk Kemi her på Danmarks Farmaceutisk Universitet. Titelen på min afhandling er: Forurening af vandmiljøet med steroidøstrogener.
Foredraget er organiseret som vist her. ….
De tre traditionelle steroidøstrogener der omtales i miljøsammenhæng er vist her. Østradiol er det naturlige hormon for mennesker og dyr og østron er en metabolit der dannes ved oxidation af østradiol, som har nogen østrogenaktivitet. Ethinyløstradiol er den østrogene komponent i alle P-piller. Inden jeg går videre vil jeg bede om at i bemærker at her har defineret forkortelser for steroidøstrogenernes navne, som jeg vil anvende gennem foredraget. Alle tre østrogener har en fælles struktur som gør at de kan bindes til østrogenreceptoren. TRYK.
Østrogener har været et af de hotteste emner indenfor toksikologi og miljøkemi i over ti år. Det skyldes især at der findes en række industrikemikalier, som uheldigvis har samme effekt som steroidøstrogenerne. Disse utilsigtede østrogener kaldes xeno-østrogener. Her er vist de vigtigste xeno-østrogener i miljøsammenhæng. Nonylphenol og octylphenol er nedbrydningsprodukter fra detergenter og bisphenol A stammer fra en række plastprodukter.
Hvad er så effekten af østrogener i vandmiljøet. Der er to typer af effekter: De kan stimulere syntese af vitellogenin og de kan forstyrre kønsdifferentieringen. Disse effekter kan forårsages både af steroidøstrogener og xeno-østrogener.
Begge typer af effekter blev fundet i vandløb i Århus amt tilbage i 2001. Den rapport der er vist her på skærmen beskriver forekomsten af østrogeneffekter i både ørreder og skaller. Desuden er der foretaget målinger af koncentrationer af alle de seks østrogener, jeg omtalte før. Desværre konkluderede rapporten at årsagen til påvirkningen af fisk var ukendt.
Miljøministeren udtalte at han ikke ville gøre noget fordi det ikke var kendt hvilket stof, der forårsager effekterne.
Jeg mener det er uholdbart at afskære sig fra at forske i og finde en løsning på et problemet fordi man ikke kan overskue det. Derfor har jeg formuleret tre spørgsmål. Er der tilstrækkeligt høje koncentrationer af nogle af østrogenerne tilstede til at forklare effekterne i vandmiljøet. Hvilke østrogener er vigtigst i vandmiljøet. Hvordan kan problemet løses. Jeg springer straks videre til at svare på de to første spørgsmål.
Jeg kunne komme et pænt stykke allerede fra skrivebordet. Der er en mængde artikler i litteraturen om hvilken koncentration der giver effekter ved eksponering af forskellige fisk for hver af østrogenerne. Det vil jeg sammenligne med koncentrationerne i udløbene fra renseanlæggene for hvert østrogen.
Jeg lavede først denne sammenligning i forbindelse med folketingets høring om ”hormonforstyrrende stoffer” i april 2002. Denne høring blev afholdt som følge af fundene af østrogenpåvirkede fisk i Århus amt. På det tidspunkt forelå to serier af målte koncentrationer. Dels resultater fra Århus amts rapport om fundet af forstyrrede fisk. Dels en lille undersøgelse jeg selv har lavet. Det ses at middelkoncentrationerne generelt er under detektionsgrænsen, så vi må basere os på maksimumkoncentrationer. De laveste effektkoncentrationer der var beskrevet ses i den midterste søjle. Til højre ses forholdet mellem de to koncentrationer. Det ses at både østron, østradiol og ethinyløstradiol findes i højere koncentration i udløbsvandet end effektgrænsen for fisk. Denne betragtning sivede hurtigt og man kunne i månederne efter se denne pointe gentaget i medierne.
Efter høringen opstod muligheder for nye projekter, så jeg kunne udebygge datagrundlaget ved analyser finansieret fra forskellige kilder. Århus amt lavede en opfølgende undersøgelse af lokaliteten Voel bæk hvor de havde fundet mange påvirkede fisk. Miljøstyrelsen lavede en undersøgelse af indløb og udløb til tre renseanlæg. Endelig lavede vi på DFU en undersøgelse af flest mulige renseanlæg over hele landet. Det ses at tendensen til at middelkoncentrationerne er under detektionsgrænsen er generel gennem alle undersøgelser.
Jeg fandt også landsdækkende data for xeno-østrogener. Der er omtrent 90 forskellige renseanlægsudløb i analyseserien. De er ikke meget forskellige fra Århus amts dataene.
Ved at kombinere alle data fås et billede af situationen baseret på alle data der er tilgængelige. Det ses at ethinyløstradiol er det vigtigste. Østron er næst, men tæt fulgt af østradiol. De tre xenoøstrogener er mindre vigtige.
For at kunne undersøge renseanlægs omsætning af sterooidøstrogener kræves analysemetoder. Jeg har lavet metoder til råt spildevand og til slam fra renseanlæg.
Jeg tog udgangspunkt i den metode til vandprøver som jeg i forvejen har anvendt. Vandprøver tilsættes en standard. Ekstraheres på en C18 kolonne. Ekstraktet oprenses med silikagel og der tilsættes endnu en standard inden analysen med GC-iontrap. Metoden kan imidlertid ikke anvendes på de anderledes og kraftigere matrice belastede prøver fra renseanlæggebe.
Her ses problemet Den problematiske matrice er således lipofil. Der satses på at der faktisk er tale om lipider.
Det er klassisk at oprense lipider med GPC, som står for Gel Permation Chromatografi. Det kaldes også størrelseskromatografi. Hvis der indføres GPC i vandmetoden fås en metode der er robust for råt spildevand. Samme oprensningsmetode viste sig også at være effektiv til at oprense solventekstrakter af slam. Jeg kan ikke på den tid der er til rådighed for foredraget nå at vise metodeevalueringen af disse metoder, men jeg vil gerne fortælle lidt om den databehandling som sikrer den høje kvalitet af analyserne. Inden vi går videre fra oversigten fra metoden skal i bemærke at der anvendes to standarder i løbet af prøveoprensningen.
Fordi der anvendes iontrap MS-MS kan fittet af et komplet datterion massespektre testes mod et reference spektre. Dette sker elektronisk ved en procedure der beregner den procentvise match mellem spektrene. Desuden testes de to vigtigste datterioners ioners indbyrdes forhold.
Desuden testes kvaliteten af hele prøvebehandlingen ved anvendelse af to parametre. ….. Begge parametre sammenlignes med middelværdien på standarderne der blev anvendt til standardkurven.
Standardkurven laves ved spiking i kildevand. Dvs. standarderne behandles over hele kurven. Her er vist en idealiseret standardkurve. Bemærk at under et vist niveau er der ikke noget signal fordi datterionmassespektret ikke har tilstrækkelig god kvalitet til at blive kvalificeret som analytisk signal. Vi definerer kvantifikationsgrænsen (LOQ) som det andet laveste punkt på den lineare del af standardkurven. Som en ekstra test sammenlignes signalet på dette punkt med baggrunsstøjen på ægte prøver. (Peak to Peak)
Før vi bevæger os videre til undersøgelsen af renseanlægget vil jeg gerne gennemgå nogle generelle pointer om om teorien omkring steroidøstrogener i renseanlæg og hvordan et moderne renseanlæg fungerer.
Mennesker udskiller ikke steroidøstrogener. Steroidøstrogener er for lipofile til at kunne udskilles over nyrerne. Derfor omdannes de til konjugerede forbindelser, ved at et enzym i kroppen sætter et sukker eller sulfatmolekyle på en hydroxygruppe. De resulterende stoffer kaldes konjugater eller konjugerede østrogener. Da de er anioner er vandopløseligheden høj og lipofiliciteten lav. De kan derfor udskilles i urinen. Konjugaterne kan spaltes så østrogenerne gendannes. Det sker både enzymatisk og ved sur hydrolyse. Der findes en række forskellige konjugater i det alle hydroxygrupper kan kobles med de to molekyler. F. eks. østradiol i begge ender.
Hvis vi zoomer ind på renseanlægget er der tale om tre typer reaktion som steroidøstrogener indgår i. Dekonjugering som gendanner østrogenet. Nedbrydning som fjerner steroidøstrogenerne. Sorption som er en reversibel proces.
Vi ser her en oversigt over steroidøstrogeners miljøkemi i forbindelse med eksponering af vandmiljøet gennem renseanlæg. Steroidøstrogener omdannes i kroppen til konjugerede østrogener, som udskilles i urinen. De konjugerede østrogener spaltes i kloakken og i renseanlægget i overvejende grad til frie steroidøstrogener. De frie østrogener nedbrydes herefter, i varierende grad efter forholdene, eller løber videre ud i vandmiljøet. I vandmiljøet har alle flercellede dyr østrogenreceptorere og forskellig følsomhed for østrogenpåvirkning.
Jeg har valgt at lave et studie af Wiesbaden renseanlæg. Wiesbaden renseanlæg er et af de første renseanlæg man har analyseret steroidøstrogener fra. Det plejer at have betydelige koncentrationer i udløbet. Da jeg målte en prøve i juni 2001 i forbindelse med at jeg hentede forskellige prøver til brug for metodeudvikling var østrogen væk. Da jeg var på anlægget var det tydeligt at der lige var afsluttet en ombygning. I den forbindelse var anlægget blevet udvidet med rensetrin for denitrifikation og biologisk fosfatfjernelse.
Her set et diagram af Wiesbaden renseanlæg fra november 2001. Vandets opholdstid er 48 timer i hele anlægget og heraf er 24 timer i aktivt slamanlægget. Aktiv slamanlægget er de tre tanke biofosfat, denitrifikation og nitrifikation, der ses øverst i midten. Vandet løbet fra venstre til højre i diagrammet. Det er vigtigt at bemærke at det cirkulerer 2-4 gange i aktiv slam anlægget Denne recirkulering har til formål at bringe nitrat tilbage til det organiske materiale. Der er to typer slam i anlægget. Stof fra primær sedimentation og overskydende aktivt slam. Det blandes og stabiliseres før fjernelse. I forbindelse med stabiliseringen af slammet frigives en del vand som pumpes tilbage i anlægget. Før ombygningen fandtes Denitrifikationstanken ikke og driften var vekslende for at få delvis denitrifikation. Slamopholdstiden var dengang under 6 dage mod nu 11-13 dage. Bemærk at prøveudtagningspunkter er angivet med sorte og hvide cirkler. De flow proportionale prøver er kun analyseret for østrogener i vandfasen, mens grab prøverne er adskilt i vand og slam som er analyseret separat.
Vandprofil: Der ses et fald med renseprocessen i de første trin. Man skal imidlertid tage højde for fortynding i biofosfattanken til omkring 1/3. Det ses tydeligt at koncentrationerne i dette trin falder mindre. Forklaringen kan være spaltning af konjugerede østrogener. – Det kommer jeg tilbage til i en massestrømsanalyse. Bemærk tilbageløbet fra slambehandlingen har høj østrogen. Slamprofil: Koncentrationer i slam fra vandbehandlingen er omtrent ens hvilket viser at tab i vandfasen ikke i nævneværdig grad skyldes sorption. I øvrigt ses høje koncentrationer i slam fra slambehandlinsgsanlægget. Det skyldes primær slam og at biomassen falder ved udrådningen.
Jeg har omregnet koncentrationerne af steroidøstrogener til massestrømme ved at gange med voluminerne afvand der flyder i gennem rensetrinnene. Desuden er de to naturlige østrogener lavet om til en sum fordi de hurtigt omdannes indbyrdes. Det ser ud som om der sker en væsentlig forøgelse af mængden af naturlige steroidøstrogener i biofosfat tanken. Det skyldes formodentlig spaltning af glucoronider. Det kommer jeg tilbage til lidt senere. I denitrifikationstrinnet nedbrydes naturlige steroidøstrogener derimod tilsyneladende fuldstændigt.
Beregningen af massestrømme er også foretaget for ethinyløstradiol. Der ses et stort tab i det første sedimentationstrin som ikke blev observeret for de naturlige østrogener. Sorption til primær slam er åbenbart vigtigere end for de naturlige. Man kunne naturligvis også forestille sig at der foregik nedbrydning i sedimentationstanken, men fra batchforsøg med slam fra anlægget blev der fundet langsommere nedbrydning af EE2 end de naturlige Ø. Resten af fjernelsen sker gradvist over alle rensetrin så der kan ikke identificeres proces forhold som er særligt favoirable for nedbrydningen.
Det næste trin I fortolkningen af dataene er en mere avanceret massebalance. Nu prøver jeg at medtage sorberede koncentrationer. Desuden har jeg tilføjet en estimeret mængde konjugerede østrogener I indløbet baseret på gennemsnitskoncentrationer fra en tysk artikel af Adler et al. (2001). Der har fundet at 65% af totalkoncentrationen er konjugert I indløbet. Denne mere avancerede massebalance viser at under 1 % af naturlige østrogener ender i udløbet og omkring 4 % ender i slammet.
Den samme avancerede massebalance for ethjinyløstradiol bliver lidt anderledes fordi kun 35% af total ethinyløstradiol er konjugeret. MAssebalancen viser at under 10 % ender i udløbet og under 4 % ender i slammet. Det bemærkes at en væsentig større andel cirkulerer med slammet i forhold til de naturlige østrogener.
Det der er ændret i Wiesbaden renseanlæg ved ombygningen er slamretentionstiden. Dvs. hvor længe bakterierne for lov at udvikle sig. Desuden er kontakttiden mellem vand og bakterier forøget.
Voel Bæk var med i Århus undersøgelsen. I denne lille bæk løber et renseanlæg ud – men SØ koncentrationerne er høje opstrøms for renseanlægget. I denne opfølgning måles koncentrationer i drænrør som er forbundet med septiktanke. Bingo!
En sidste ting jeg vil vise inden vi går videre til renseanlægget er en skitse af de generelle strømme af vand og slam i et renseanlæg. Der er to typer slam i anlægget. Stof fra primær sedimentation og overskydende aktivt slam. Det blandes og stabiliseres før fjernelse. Vandet løber desuden ikke direkte gennem anlægget men cirkulerer et par gange i aktiv slam anlægget for at bringe nitrat tilbage til det organiske materiale.