ISO 5667-3:2012
(Main)Water quality — Sampling — Part 3: Preservation and handling of water samples
Water quality — Sampling — Part 3: Preservation and handling of water samples
ISO 5667-3:2012 establishes general requirements for sampling, preservation, handling, transport and storage of all water samples including those for biological analyses. It is not applicable to water samples intended for microbiological analyses as specified in ISO 19458, ecotoxicological assays, biological assays, and passive sampling as specified in the scope of ISO 5667-23. ISO 5667-3:2012 is particularly appropriate when spot or composite samples cannot be analysed on site and have to be transported to a laboratory for analysis.
Qualité de l'eau — Échantillonnage — Partie 3: Conservation et manipulation des échantillons d'eau
L'ISO 5667-3:2012 établit les exigences générales relatives à l'échantillonnage, la conservation, la manipulation, le transport et le stockage de tous les échantillons d'eau, y compris ceux destinés à des analyses biologiques. Elle ne s'applique pas aux échantillons d'eau destinés à des analyses microbiologiques telles que spécifiées dans l'ISO 19458, des essais écotoxicologiques, des essais biologiques et ni à l'échantillonnage passif tel que spécifié dans le domaine d'application de l'ISO 5667‑23. L'ISO 5667-3:2012 s'applique en particulier chaque fois qu'un échantillon ponctuel ou composite ne peut être analysé sur site et doit être transporté vers un laboratoire pour analyse.
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МЕЖДУНАРОДНЫЙ ISO
СТАНДАРТ 5667-3
Четвертое издание
2012-11-15
Качество воды. Отбор проб.
Часть 3. Консервация и обработка проб
воды
Water quality — Sampling —
Part 3. Preservation and handling of water samples
Ответственность за подготовку русской версии несѐт GOST R
(Российская Федерация) в соответствии со статьѐй 18.1 Устава ISO
Ссылочный номер
ISO 5667-3:2012(R)
©
ISO 2012
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ISO 5667-3:2012(R)
ДОКУМЕНТ ЗАЩИЩЕН АВТОРСКИМ ПРАВОМ
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ISO 5667-3:2012(R)
Содержание Страница
Предисловие. iv
Введение . vi
1 Область применения . 1
2 Нормативные ссылки . 1
3 Термины и определения . 2
4 Отбор проб и цепь обеспечения сохранности проб. 2
5 Реактивы и материалы . 3
5.1 Твердые вещества . 3
5.2 Растворы . 4
5.3 Материалы . 5
6 Контейнеры . 5
6.1 Выбор и подготовка контейнера . 5
6.2 Фильтрация на месте . 5
6.3 Заполнение контейнера . 6
7 Обработка и консервация проб . 6
7.1 Обработка и консервация проб для физических и химических исследований . 6
7.2 Обработка и консервация проб для биологических исследований. 7
7.3 Обработка и консервация проб для радиохимического анализа . 7
8 Транспортировка проб . 8
9 Идентификация проб . 8
10 Прием проб . 9
11 Хранение проб . 9
Приложение А (информативное) Методы консервации проб . 11
Приложение B (информативное) Подготовка контейнера. 39
Приложение С (информативное) Протокол, используемый при исследованиях валидации,
проведенных в Нидерландах . 40
Библиография . 42
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ISO 5667-3:2012(R)
Предисловие
Международная организация по стандартизации (ISO) является всемирной федерацией национальных
организаций по стандартизации (комитетов-членов ISO). Разработка международных стандартов
обычно осуществляется техническими комитетами ISO. Каждый комитет-член ISO, заинтересованный
в деятельности, для которой был создан технический комитет, имеет право быть представленным в
этом комитете. Международные организации, правительственные и неправительственные, имеющие
связи с ISO, также принимают участие в работах. ISO непосредственно сотрудничает с
Международной электротехнической комиссией (IEC) по всем вопросам электротехнической
стандартизации.
Международные стандарты разрабатываются в соответствии с правилами, приведенными в
Директивах ISO/IEC, Часть 2.
Основная задача технических комитетов состоит в подготовке международных стандартов. Проекты
международных стандартов, одобренные техническими комитетами, рассылаются комитетам-членам
на голосование. Их опубликование в качестве международных стандартов требует одобрения, по
меньшей мере, 75 % комитетов-членов, принимающих участие в голосовании.
Следует иметь в виду, что некоторые элементы настоящего документа могут быть объектом патентных
прав. ISO не должен нести ответственность за идентификацию какого-либо одного или всех патентных
прав.
Международный стандарт ISO 5667-3 разработан Техническим комитетом ISO/TC 147, Качество воды,
Подкомитетом SC 6, Отбор проб (общие методы).
Настоящее четвертое издание отменяет и заменяет третье издание (ISO 5667-3:2003), которое
подверглось техническому пересмотру.
ISO 5667 состоит из следующих частей под общим заголовком Качество воды. Отбор проб:
Часть 1. Руководство по составлению программ и методик отбора проб
Часть 3. Консервация и обработка проб воды
Часть 4. Руководство по отбору проб из естественных и искусственных озер
Часть 5. Руководство по отбору проб питьевой воды из водоочистных станций и
трубопроводных распределительных систем
Часть 6. Руководство по отбору проб из рек и потоков
Часть 7. Руководство по отбору проб воды и пара из котельных установок
Часть 8. Руководство по отбору проб влажных осаждений
Часть 9. Руководство по отбору проб морской воды
Часть 10. Руководство по отбору проб из сточных вод
Часть 11. Руководство по отбору проб грунтовых вод
Часть 12. Руководство по отбору проб из донных отложений
Часть 13. Руководство по отбору проб шлама
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ISO 5667-3:2012(R)
Часть 14. Руководство по обеспечению качества при отборе и обработке проб природных вод
Часть 15. Руководство по консервации и обработке проб осадка и отложений
Часть 16. Руководство по биотестированию проб
Часть 17. Руководство по отбору валовых проб взвешенных твердых частиц
Часть 19. Руководство по отбору проб в морских отложениях
Часть 20. Руководство по использованию выборочных данных для принятия решения.
Соответствие порогам и классификационным системам
Часть 21. Руководство по отбору проб питьевой воды, распределяемой танкерами или другими
системами, кроме водопроводных труб
Часть 22. Руководство по проектированию и установке пунктов мониторинга качества
грунтовых вод
Часть 23. Руководство по пассивному отбору проб из поверхностных вод
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ISO 5667-3:2012(R)
Введение
Настоящая часть ISO 5667 предназначена для использования совместно с ISO 5657-1, в котором
рассматриваются вопросы составления программ и методик отбора проб воды.
Там, где это возможно, содержание этой части ISO 5667 было приведено в соответствие с
действующими стандартами. Если новые исследования или результаты валидации давали новое
представление о рассматриваемом вопросе, то использовались самые последние знания.
[63]
Руководство по протоколам валидации можно найти в ISO Guide 34.
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МЕЖДУНАРОДНЫЙ СТАНДАРТ ISO 5667-3:2012(R)
Качество воды. Отбор проб.
Часть 3. Консервация и обработка проб воды
ЗАМЕЧАНИЕ — Настоящая часть ISO 5667 и международные стандарты на методы анализа,
перечисленные в Приложении A, дополняют друг друга. В том случае, когда международный
стандарт на методы анализа не применим, метод(ы), описанные в Таблицах A.1 – A.3,
приобретает(ют) нормативный статус.
При разработке новых или пересмотренных стандартов на методы анализа, в которых время
хранения и методы консервации проб воды отличаются от указанных в Таблицах A.1 – A.3, эти
время хранения и методы консервации должны быть аттестованы и представлены в ISO/TC
147/SC 6/WG 3 для включения следующий пересмотр данной части ISO 5667.
1 Область применения
В настоящей части ISO 5667 устанавливаются общие требования к отбору проб, консервации,
обработке, транспортировке и хранению всех проб воды, включая пробы для биологического анализа.
Этот стандарт не применим к пробам воды, предназначенным для микробиологического анализа, как
указано в ISO 19458, экотоксилогическим пробам, биологическим пробам и пассивному отбору проб,
как установлено в области применения ISO 5667-23.
Применение данной части ISO 5667 особенно уместно в том случае, когда локальные или усредненные
пробы не могут быть подвергнуты анализу на месте, а должны быть доставлены в лабораторию для
проведения анализа.
2 Нормативные ссылки
Следующие ссылочные нормативные документы являются обязательными при применении данного
документа. Для жестких ссылок применяется только цитированное издание документа. Для плавающих
ссылок необходимо использовать самое последнее издание нормативного ссылочного документа
(включая любые изменения).
ISO 3696, Вода для лабораторного анализа. Технические требования и методы испытаний
ISO 5667 (все части), Качество воды. Отбор проб
ISO 19458, Качество воды. Отбор проб для микробиологического анализа
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ISO 5667-3:2012(R)
3 Термины и определения
Применительно к данному документу используются следующие термины и определения.
3.1
целостность
integrity
свойство, при котором рассматриваемые параметр(ы), информация или содержимое контейнера для
проб не должны быть изменены или потеряны несанкционированным образом или не должны терять
свою репрезентативность
3.2
консервация пробы
sample preservation
любая методика, используемая для стабилизации пробы таким способом, чтобы исследуемые
свойства поддерживались стабильными от стадии сбора до стадии подготовки для анализа
[29]
[ISO 11074:2005, 4.4.20]
ПРИМЕЧАНИЕ Для несхожих аналитов может потребоваться несколько проб из одного и того же источника,
которые стабилизируют по различным методикам.
3.3
хранение пробы
sample storage
процесс и результат сохранения пробы, пригодной в предписанных условиях в течение (обычно)
заданного интервала времени от сбора пробы до ее дальнейшей обработки
[29]
ПРИМЕЧАНИЕ 1 Адаптировано из ISO 11074:2005, 4.4.22.
ПРИМЕЧАНИЕ 2 Заданное время представляет собой максимальный интервал времени.
3.4
время хранения
storage time
период времени между заполнением контейнера для проб и дальнейшей обработкой пробы в
лаборатории, если она хранится в предписанных условиях
ПРИМЕЧАНИЕ 1 Отбор проб закончен, как только контейнер заполнен пробой. Время хранения заканчивается,
когда проба отбирается аналитиком, чтобы начать подготовку пробы перед анализом.
ПРИМЕЧАНИЕ 2 Дальнейшая обработка для большинства аналитов состоит в экстрагировании растворителем
или разложении кислотой. Начальные стадии подготовки пробы могут быть стадиями, дополняющими условия
хранения для поддержания концентраций аналита.
4 Отбор проб и цепь обеспечения сохранности проб
В случае необходимости отбора проб, они отбираются в соответствии с программой отбора проб.
Первой стадией является разработка программы отбора проб. Руководство по этому вопросу дается в
ISO 5667-1.
В зависимости от типа пробы и ее матрицы необходимо принимать во внимание руководящие
указания, описанные в соответствующей(их) части(ях) ISO 5667 и ISO 19458.
Процесс консервации и обработки проб воды включает несколько стадий. Во время этого процесса
ответственность за пробы может меняться. Чтобы гарантировать целостность проб, все стадии этого
процесса должны быть задокументированы.
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ISO 5667-3:2012(R)
Все методики подготовки должны проверяться, чтобы гарантировать отсутствие положительного или
отрицательного мешающего воздействия. Как минимум, они должны включать анализ холостых проб
(например, полевой холостой пробы или контейнера для проб) или проб, содержащих известные
уровни соответствующих аналитов, как указано в ISO 5667-14.
5 Реактивы и материалы
ПРЕДУПРЕЖДЕНИЕ — Некоторые консерванты (например, кислоты, щелочи, формальдегид)
следует использовать с осторожностью. Персонал, занятый отбором проб, должен быть
предупрежден о потенциальных опасностях и о мерах предосторожности, которые необходимо
соблюдать.
Ниже перечислены реактивы, которые используются для консервации проб и должны готовиться
только в соответствии с требованиями для конкретных процедур отбора проб. Если иное не указано,
все используемые реактивы должны быть по меньшей мере аналитической степени чистоты, а вода
должна, как минимум, соответствовать классу чистоты 2 по ISO 3696. Кислоты, упоминаемые в этой
части ISO 5667 — это имеющиеся в продаже "концентрированные" кислоты.
Все реактивы должны иметь этикетки с указанием срока годности. Срок годности представляет собой
период, в течение которого реактив пригоден к использованию при условии правильного хранения.
Этот срок годности не должен превышаться. Все реактивы, не полностью использованные ко времени
окончания срока годности, должны выбрасываться.
ПРИМЕЧАНИЕ Часто срок годности реактивов обеспечивает получающая лаборатория.
Периодически проверяют реактивы, например, с помощью полевых холостых проб, и выбрасывают
любой реактив, найденный непригодным.
В промежутке между выездами на место отбора проб реактивы должны храниться отдельно от
контейнеров для отбора проб и другого оборудования в чистых закрытых шкафах, чтобы исключить их
загрязнение.
Каждая проба после добавления консерванта должна быть промаркирована соответствующим
образом. В противном случае не будет видимых признаков в отношении того, какие пробы были
подвергнуты консервации, а какие нет.
5.1 Твердые вещества
5.1.1 Тиосульфат натрия, пентагидрат, Na S O ·5H O, w(Na S O ·5H O) > 99 %.
2 2 3 2 2 2 3 2
5.1.2 Аскорбиновая кислота, C H O , w(C H O ) > 99 %.
6 8 6 6 8 6
5.1.3 Гидроксид натрия, NaOH, w(NaOH) > 99 %.
5.1.4 Тетраборат натрия, декагидрат, Na B O ·10H O, w(Na B O ·10H O), > 99 %.
2 4 7 2 2 4 7 2
ПРЕДУПРЕЖДЕНИЕ — Декагидрат тетробората натрия известен как канцерогенное, мутагенное и
токсичное вещество, влияющее на репродуктивную функцию (CMR).
5.1.5 Гексаметилентетрамин (гексамин, уротропин), C H N , w(C H N ) > 99 %.
6 12 4 6 12 4
5.1.6 Йодид калия, KI, w(KI) > 99 %.
5.1.7 Йод, I w(I ) > 99 %.
2, 2
5.1.8 Ацетат натрия, C H NaO , w(C H NaO ) > 99 %.
2 3 2 2 3 2
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ISO 5667-3:2012(R)
5.1.9 Этилендиамин, C H N , w(C H N ) > 99 %.
2 8 2 2 8 2
5.2 Растворы
5.2.1 Раствор ацетата цинка C H O Zn (концентрацией 10 г/л).
4 6 4
Растворяют 10,0 г ацетата цинка в 100 мл воды. Разбавляют до 100 мл водой. Хранят раствор в
полиэтиленовой или стеклянной бутылке в течение максимального периода времени 1 год.
5.2.2 Ортофосфорная кислота (ρ ≈ 1,7 г/мл), H PO , w(H PO ) > 85 %, c(H PO ) = 15 моль/л.
3 4 3 4 3 4
5.2.3 Соляная кислота (ρ ≈ 1,2 г/мл), HCl, w(HCl) > 36 %, c(HCl) = 12,0 моль/л.
5.2.4 Азотная кислота (ρ ≈ 1,42 г/мл), HNO , w(HNO ) > 65 %, c(HNO ) = 15,8 моль/л.
3 3 3
5.2.5 Серная кислота (ρ ≈ 1,84 г/мл), H SO (свежеприготовленная).
2 4
Разбавляют концентрированную серную кислоту (H SO ), ρ ≈ 1,84 г/мл w(H SO ) ≈ 98 % 1 + 1 путем
2 4 2 4
осторожного добавления концентрированной кислоты к равному объему воды и перемешивают.
ПРЕДОСТЕРЕЖЕНИЕ — Добавление концентрированной кислоты к воде может вызвать бурную
реакцию, потому что эта реакция является экзотермической.
5.2.6 Раствор гидроксида натрия (ρ ≈ 0,40 г/мл), NaOH.
5.2.7 Раствор формальдегида (формалин), CH O, (CH O) = 37 % – 40 % (свежеприготовленный).
2 2
ПРЕДОСТЕРЕЖЕНИЕ — Следует опасаться паров формальдегида. Не храните большое
количество проб в небольших рабочих помещениях.
5.2.8 Динатриевая соль этилендиаминтетрауксусной кислоты (EDTA) (ρ ≈ 0,025 г/мл),
C H N Na O ⋅2H O, w(C H N Na O ⋅2H O) > 99 %.
10 14 2 2 8 2 10 14 2 2 8 2
Растворяют 25 г EDTA в 1 000 мл воды.
5.2.9 Этанол C H OH, (C H OH) = 96 %.
2 5 2 5
5.2.10 Щелочной раствор Люголя, растворяют 100 г йодида калия (5.1.6), 50 г йода (5.1.7) и 250 г
ацетата натрия (5.1.8) в 1 000 мл воды до pH 10.
5.2.11 Кислый раствор Люголя, растворяют 100 г йодида калия (5.1.6), 50 г йода (5.1.7) и 100 мл
ледяной уксусной кислоты (5.2.17) в 1 000 мл воды до pH 2.
5.2.12 Нейтрализованный раствор формальдегида, раствор формальдегида (5.2.7),
нейтрализованный тетраборатом натрия (5.1.4) или гексаметилентетрамином (5.1.5). Раствор
формалина концентрацией 100 г/л дает концентрацию конечного раствора (CH O) = 3,7 % – 4,0 %.
2
ПРЕДОСТЕРЕЖЕНИЕ — Следует опасаться паров формальдегида. Не храните большое
количество проб в небольших рабочих помещениях.
5.2.13 Этанольный консервирующий раствор.
Смешивают этанол (5.2.9), раствор формальдегида (5.2.7) и глицерин (5.2.18) (100 + 2 + 1 частей по
объему, соответственно).
5.2.14 Гипохлорит натрия NaOCl, w(NaOCl) = 10 %. Растворяют 100 г гипохлорита натрия (NaOCl) в
1 000 мл воды.
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ISO 5667-3:2012(R)
5.2.15 Йодат калия KIO , w(KIO ) = 10 %. Растворяют 100 г йодата калия (KIO ) в 1 000 мл воды.
3 3 3
5.2.16 Метановая кислота (муравьиная кислота) CH O , (CH O ) > 98 %.
2 2 2 2
5.2.17 Ледяная уксусная кислота C H O , w(C H O ) > 99 %.
2 4 2 2 4 2
5.2.18 Глицерин C H (OH) .
3 5 3
5.3 Материалы
5.3.1 Контейнер и крышка, типы которых указаны в Таблицах A.1 – A.3.
5.3.2 Фильтр, с размером пор от 0,40 мкм до 0,45 мкм, если не установлен фильтр с другим
размером пор в международном стандарте на методы анализа.
6 Контейнеры
6.1 Выбор и подготовка контейнера
Выбор и подготовка контейнера имеют весьма важное значение и в ISO 5667-1 дается руководство по
этому вопросу.
Сведения о типе используемого для сбора и хранения проб контейнера приведены в Таблицах A.1 – A.3.
При выборе материала прокладки крышки контейнера следует руководствоваться теми же
соображениями, что и при выборе материала соответствующего контейнера.
Контейнеры для проб должны быть изготовлены из материала, пригодного для консервации
природных свойств как пробы, так и ожидаемого диапазона загрязняющих веществ. Соответствующие
типы контейнеров для каждого аналита, подлежащего измерению, приводятся в Таблицах A.1 – A.3.
ПРИМЕЧАНИЕ В случае очень низких концентрация металлов предписанные контейнеры могут отличаться от
контейнеров, используемых для более высоких концентраций. Подробности можно найти в Таблице A.1 или в
международных стандартах на методы анализа.
Если проба подлежит замораживанию, для предотвращения разрушения должны использоваться
соответствующие контейнеры, например, из полиэтилена (PE) или политетрафторэтилена (PTFE).
Предпочтительно использование одноразовых контейнеров. Некоторые производители поставляют
контейнеры вместе с сертификатом чистоты. Если такие сертификаты чистоты поставляются, то нет
необходимости очищать или промывать контейнеры перед использованием.
6.2 Фильтрация на месте
В некоторых случаях необходима фильтрация на месте.
Грунтовые воды должны быть отфильтрованы на месте в том случае, если анализу подлежат
растворенные металлы.
Вода должна быть отфильтрована (5.3.2) на месте в том случае, если это требуется согласно
Приложению A. Если не указано иначе, должен использоваться фильтр с размером пор от 0,40 мкм
до 0,45 мкм.
Если непосредственная фильтрация на месте невозможна, то в протоколе испытания должна быть
указана причина этого и период времени между отбором проб и фильтрацией.
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ISO 5667-3:2012(R)
6.3 Заполнение контейнера
Контейнер (5.3.1) должен быть заполнен полностью, если иначе не предписано в Таблицах A.1 – A.3
или в используемом международном стандарте на методы анализа. Если пробы подлежат
замораживанию, которое является составной частью их консервации, то контейнер для проб не
должен заполняться полностью. Это необходимо для предотвращения его разрушения, которое может
возникнуть в результате расширения льда во время процесса замораживания и оттаивания.
Если в бутылке отсутствуют консервирующие средства, то рекомендуется предварительно промыть
ее. Руководство по предварительной промывке можно найти в ISO 5667-14.
7 Обработка и консервация проб
7.1 Обработка и консервация проб для физических и химических исследований
Состав вод, особенно пресных, сточных и грунтовых вод, может меняться в результате физических,
химических или биологических реакций, которые могут произойти между временем отбора проб и
началом анализа. Природа и скорость этих реакций часто такова, что, если не принять мер
предосторожности во время отбора проб, их транспортировки и хранения (для конкретных аналитов),
то определенные при анализе концентрации будут отличаться от концентраций, существующих во
время отбора проб.
Степень этих изменений зависит от химической и биологической природы пробы, ее температуры,
воздействия на нее света, типа контейнера, в который она помещена, времени, прошедшего от
момента отбора пробы до анализа, и условий, которым она подвергается, например, перемешиванию
при транспортировке. Другие специфические причины, которые могут вызвать изменения,
перечислены в a) – f).
a) Наличие бактерий, водорослей и других организмов, которые могут потреблять некоторые
компоненты пробы. Эти организмы могут также изменять природу этих компонентов с
образованием новых компонентов. Такая биологическая активность влияет, например, на
концентрации растворенного кислорода, диоксида углерода, соединений азота, фосфора и иногда
кремния.
b) Некоторые соединения могут окисляться либо растворенным кислородом, присутствующим в
пробах, либо атмосферным кислородом [например, органические соединения, Fe (II) и сульфиды].
c) Некоторые соединения могут осаждаться из раствора, например, карбонат кальция, металлы и их
соединения, такие как Al(OH) , или теряться вследствие перехода в газовую фазу (например,
3
кислород, цианиды и ртуть).
d) Поглощение диоксида углерода из воздуха может изменять рН, удельную электропроводность и
концентрацию растворенного диоксида углерода. Прохождение таких соединений, как аммиак и
фторид кремния, через некоторые типы пластмасс также может оказывать влияние на рН и
удельную электропроводность.
e) Растворенные металлы или металлы в коллоидном состоянии, а также некоторые органические
соединения могут необратимо адсорбироваться на поверхности контейнеров или твердых
материалов в пробах.
f) Возможна деполимеризация полимеров и, наоборот, полимеризация простых соединений.
Изменение конкретных компонентов происходит в различной степени и с различной скоростью не
только в зависимости от типа воды, но также, в случае воды одного и того же типа, в зависимости от
сезонных условий.
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ISO 5667-3:2012(R)
Эти изменения часто происходят достаточно быстро, так что состав пробы за короткое время
значительно меняется. Во всех случаях важно принять меры предосторожности, чтобы свести к
минимуму эти реакции и, в случае большого числа аналитов, выполнять анализ пробы с минимальной
задержкой. В том случае, если фильтрация на месте является необходимой мерой предосторожности
в отношении этих изменений, то должен использоваться фильтр, указанный в (5.3.2).
Подробности консервации проб приводятся в Таблице A.1.
7.2 Обработка и консервация проб для биологических исследований
Обработка проб для биологических исследований отличается от обработки проб, предназначенных
для химического анализа. Можно использовать добавление к пробам для биологического
исследования химических веществ для фиксации и/или консервации пробы. Термин "фиксация"
используется для описания защиты морфологических структур, в то время как термин "консервация"
относится к защите органических веществ от биохимического или химического разложения.
Консерванты, по определению, токсичны и добавление консервантов может привести к гибели живых
организмов. Перед их гибелью раздражение наиболее чувствительных организмов, не имеющих
плотных клеточных стенок, может привести к их сплющиванию, прежде чем будет завершена
фиксация. Чтобы свести к минимуму этот эффект, важно, чтобы фиксирующий агент быстро проникал
в клетку.
ВАЖНОЕ ЗАМЕЧАНИЕ — Кислые растворы Люголя (5.2.11) могут привести к потере структур в
организмах, а также к потере мелких организмов (например, некоторых жгутиковых); в этом
случае используют щелочной раствор Люголя (5.2.10), например, в летний период, когда часто
наблюдается присутствие силико-жгутиковых.
Фиксация и/или консервация проб для биологического исследования должна соответствовать
следующим критериям:
а) воздействие фиксатора и/или консерванта на конкретный организма должно быть известно
заранее;
b) фиксатор и/или консервант должен эффективно предотвращать биологическое разложение
органического вещества, по крайней мере, в период хранения проб;
c) фиксатор и/или консервант должен давать возможность проводить оценку биологического
аналита (например, организмов или таксономических групп) в течение периода хранения проб.
Подробности консервации проб приводятся в Таблице A.2.
7.3 Обработка и консервация проб для радиохимического анализа
ПРЕДУПРЕЖДЕНИЕ — Может быть необходима радиационная защита, например,
экранирование, которая зависит от активности пробы.
Имеется небольшое различие в обработке проб для радиохимического и для физико-химического
анализов.
Задержка между отбором проб и измерением должна быть совместима с периодом полураспада
определяемого радионуклида. Условия, выбранные для адекватного хранения, не зависят от периода
полураспада радионуклида, но идентичны условиям, необходимым для соответствующего устойчивого
изотопа.
ПРИМЕЧАНИЕ Охлаждение радиологических проб используется, главным образом, для предотвращения
роста водорослей и биологической порчи. При проведении радиохимических анализов нет необходимости в
стадии консервации. Эти пробы часто объединяют с пробами для физического, химического или биологического
анализа.
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ISO 5667-3:2012(R)
8 Транспортировка проб
Процедуры охлаждения или замораживания должны применяться к пробам для увеличения периода
времени, доступного для транспортировки и хранения, и, если это требуется согласно Таблиц A.1 –
A.3. Если имеет место транспортировка, то план отбора проб (например, ISO 5667-1) должен
учитывать:
время между отбором проб и началом транспортировки;
время транспортировки;
время начала анализа в лаборатории.
Суммарное значение этих трех периодов ограничено максимальным временем хранения в
соответствии с Таблицами A.1 – A.3.
В том случае, если максимальное время хранения не может соответствовать этому значению, то план
отбора проб должен быть переработан, чтобы эти требования были включены.
Было установлено, что температура охлаждения в холодильнике во время транспортировки (5 ± 3) °C
пригодна для большинства применений. Применяемые процедуры охлаждения и замораживания
должны соответствовать рекомендациям, полученным от аналитических лабораторий. Особенно при
замораживании необходим детальный контроль процесса замораживания и оттаивания для того,
чтобы вернуть пробу к ее исходному равновесию после оттаивания.
Контейнеры, содержащие пробы, должны быть защищены и герметизированы во время
транспортировки таким образом, чтобы пробы не подвергались порче или потере какой-либо части их
содержимого. Упаковка контейнеров должна защищать их от возможного наружного загрязнения,
особенно рядом с местом вскрытия, а также сама упаковка не должна быть источником загрязнения.
Стеклянные контейнеры должны быть защищены от возможного разрушения во время
транспортировки с помощью соответствующей упаковки. Пробы должны транспортироваться как
можно скорее после отбо
...
INTERNATIONAL ISO
STANDARD 5667-3
Fourth edition
2012-11-15
Water quality — Sampling —
Part 3:
Preservation and handling of water
samples
Qualité de l’eau — Ėchantillonnage —
Partie 3: Conservation et la manipulation des échantillions d’eau
Reference number
ISO 5667-3:2012(E)
©
ISO 2012
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ISO 5667-3:2012(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2012
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
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Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
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Published in Switzerland
ii © ISO 2012 – All rights reserved
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ISO 5667-3:2012(E)
Contents Page
Foreword .iv
Introduction .vi
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Sampling and chain of custody . 2
5 Reagents and materials . 2
5.1 Solids . 3
5.2 Solutions . 3
5.3 Materials . 4
6 Containers . 4
6.1 Container selection and preparation . 4
6.2 Filtration on site . 5
6.3 Filling the container . 5
7 Sample handling and preservation . 5
7.1 Sample handling and preservation for physical and chemical examination . 5
7.2 Sample handling and preservation for biological examination . 6
7.3 Sample handling and preservation for radiochemical analysis . 6
8 Sample transport . 7
9 Identification of samples . 7
10 Sample reception . 8
11 Sample storage . 8
Annex A (informative) Techniques for sample preservation . 9
Annex B (informative) Container preparation .35
Annex C (informative) Protocol as used in Dutch validation studies .36
Bibliography .38
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ISO 5667-3:2012(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International
Standards adopted by the technical committees are circulated to the member bodies for voting.
Publication as an International Standard requires approval by at least 75 % of the member bodies
casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 5667-3 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 6,
Sampling (general methods).
This fourth edition cancels and replaces the third edition (ISO 5667-3:2003), which has been
technically revised.
ISO 5667 consists of the following parts, under the general title Water quality — Sampling:
— Part 1: Guidance on the design of sampling programmes and sampling techniques
— Part 3: Preservation and handling of water samples
— Part 4: Guidance on sampling from lakes, natural and man-made
— Part 5: Guidance on sampling of drinking water from treatment works and piped distribution systems
— Part 6: Guidance on sampling of rivers and streams
— Part 7: Guidance on sampling of water and steam in boiler plants
— Part 8: Guidance on the sampling of wet deposition
— Part 9: Guidance on sampling from marine waters
— Part 10: Guidance on sampling of waste waters
— Part 11: Guidance on sampling of groundwaters
— Part 12: Guidance on sampling of bottom sediments
— Part 13: Guidance on sampling of sludges
— Part 14: Guidance on quality assurance of environmental water-sampling and handling
— Part 15: Guidance on the preservation and handling of sludge and sediment samples
— Part 16: Guidance on biotesting of samples
— Part 17: Guidance on sampling of bulk suspended solids
— Part 19: Guidance on sampling of marine sediments
iv © ISO 2012 – All rights reserved
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ISO 5667-3:2012(E)
— Part 20: Guidance on the use of sampling data for decision making — Compliance with thresholds and
classification systems
— Part 21: Guidance on sampling of drinking water distributed by tankers or means other than
distribution pipes
— Part 22: Guidance on the design and installation of groundwater monitoring points
— Part 23: Guidance on passive sampling in surface waters
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ISO 5667-3:2012(E)
Introduction
This part of ISO 5667 is intended to be used in conjunction with ISO 5667-1, which deals with the design
of sampling programmes and sampling techniques.
Where possible this part of ISO 5667 has been brought into line with current standards. Where new
research or validation results have provided new insights, the latest knowledge has been used.
[63]
Guidance on validation protocols can be found in ISO Guide 34.
vi © ISO 2012 – All rights reserved
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INTERNATIONAL STANDARD ISO 5667-3:2012(E)
Water quality — Sampling —
Part 3:
Preservation and handling of water samples
NOTICE — This part of ISO 5667 and the analytical International Standards listed in Annex A
are complementary. Where no analytical International Standard is applicable, the technique(s)
described in Tables A.1 to A.3 take(s) normative status.
When new or revised analytical standards are developed with storage times or preservative
techniques differing from those in Tables A.1 to A.3, then the storage times or preservative
techniques should be validated and presented to ISO/TC 147/SC 6/WG 3 for incorporation into
the next revision of this part of ISO 5667.
1 Scope
This part of ISO 5667 establishes general requirements for sampling, preservation, handling, transport
and storage of all water samples including those for biological analyses. It is not applicable to water
samples intended for microbiological analyses as specified in ISO 19458, ecotoxicological assays,
biological assays, and passive sampling as specified in the scope of ISO 5667-23.
This part of ISO 5667 is particularly appropriate when spot or composite samples cannot be analysed on
site and have to be transported to a laboratory for analysis.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 5667 (all parts), Water quality — Sampling
ISO 19458, Water quality — Sampling for microbiological analysis
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
integrity
property that the parameter(s) of interest, information or content of the sample container has not been
altered or lost in an unauthorized manner or subject to loss of representativeness
3.2
sample preservation
any procedure used to stabilize a sample in such a way that the properties under examination are
maintained stable from the collection step until preparation for analysis
[29]
[ISO 11074:2005, 4.4.20]
NOTE Different analytes may require several samples from the same source that are stabilized by
different procedures.
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ISO 5667-3:2012(E)
3.3
sample storage
process, and the result, of keeping a sample available under predefined conditions for a (usually)
specified time interval between collection and further treatment of a sample
[29]
NOTE 1 Adapted from ISO 11074:2005, 4.4.22.
NOTE 2 Specified time is the maximum time interval.
3.4
storage time
period of time between filling of the sample container and further treatment of the sample in the
laboratory, if stored under predefined conditions
NOTE 1 Sampling finishes as soon as the sample container has been filled with the sample. Storage time ends
when the sample is taken by the analyst to start sample preparation prior to analysis.
NOTE 2 Further treatment is, for most analytes, a solvent extraction or acid destruction. The initial steps
of sample preparation can be steps complementary to the storage conditions for the maintenance of analyte
concentrations.
4 Sampling and chain of custody
If there is a need to take samples, this is done according to a sampling programme. The first step is to
design a sampling programme. Guidance on this topic is given in ISO 5667-1.
Depending on the sample type and matrix, the guidelines found in the relevant part(s) of ISO 5667 and
ISO 19458 shall be consulted.
The process of preservation and handling of water samples consists of several steps. During this
process, the responsibility for the samples might change. To ensure the integrity of the samples, all steps
involving the sample shall be documented.
All preparation procedures shall be checked to ensure positive or negative interferences do not occur.
As a minimum, this shall include the analysis of blanks (e.g. field blank or sample container) or samples
containing known levels of relevant analytes as specified in ISO 5667-14.
5 Reagents and materials
WARNING — Certain preservatives (e.g. acids, alkalis, formaldehyde) need to be used with
caution. Sampling personnel should be warned of potential dangers, and appropriate safety
procedures should be followed.
The following reagents are used for the sample preservation and shall only be prepared according to
individual sampling requirements. All reagents used shall be of at least analytical reagent grade and
water shall be of at least ISO 3696, grade 2. Acids referred to in this part of ISO 5667 are commercially
available “concentrated” acids.
All reagents shall be labelled with a “shelf-life”. The shelf-life represents the period for which the reagent
is suitable for use, if stored correctly. This shelf-life shall not be exceeded. Any reagents that are not
completely used by the expiry of the shelf-life date shall be discarded.
NOTE Often the shelf-life of reagents is supplied by the receiving laboratory.
Check reagents periodically, e.g. by field blanks, and discard any reagent found to be unsuitable.
Between on-site visits, reagents shall be stored separately from sample containers and other equipment
in a clean, secure cabinet in order to prevent contamination.
Each sample shall be labelled accordingly, after the addition of the preservative. Otherwise, there could
be no visible indication as to which samples have been preserved, and which have not.
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ISO 5667-3:2012(E)
5.1 Solids
5.1.1 Sodium thiosulfate pentahydrate, Na S O ·5H O, w(Na S O ·5H O) > 99 %.
2 2 3 2 2 2 3 2
5.1.2 Ascorbic acid, C H O , w(C H O ) > 99 %.
6 8 6 6 8 6
5.1.3 Sodium hydroxide, NaOH, w(NaOH) > 99 %.
5.1.4 Sodium tetraborate decahydrate, Na B O ·10H O, w(Na B O ·10H O), > 99 %.
2 4 7 2 2 4 7 2
CAUTION Sodium tetraborate decahydrate is known to be a carcinogen, mutagen and
reproductive toxin (CMR).
5.1.5 Hexamethylenetetramine (hexamine, urotropine), C H N , w(C H N ) > 99 %.
6 12 4 6 12 4
5.1.6 Potassium iodide, KI, w(KI) > 99 %.
5.1.7 Iodine, I , w(I ) > 99 %.
2 2
5.1.8 Sodium acetate, C H NaO , w(C H NaO ) > 99 %.
2 3 2 2 3 2
5.1.9 Ethylenediamine, C H N , w(C H N ) > 99 %.
2 8 2 2 8 2
5.2 Solutions
5.2.1 Zinc acetate solution C H O Zn (10 g/l).
4 6 4
Dissolve 10,0 g of zinc acetate in ∼100 ml of water . Dilute to 100 ml with water. Store the solution in a
polypropylene or glass bottle for a maximum period of 1 a.
5.2.2 Orthophosphoric acid (ρ ≈ 1,7 g/ml), H PO , w(H PO ) > 85 %, c(H PO ) = 15 mol/l.
3 4 3 4 3 4
5.2.3 Hydrochloric acid (ρ ≈ 1,2 g/ml), HCl, w(HCl) > 36 %, c(HCl) = 12,0 mol/l.
5.2.4 Nitric acid (ρ ≈ 1,42 g/ml), HNO , w(HNO ) > 65 %, c(HNO ) = 15,8 mol/l.
3 3 3
5.2.5 Sulfuric acid (ρ ≈ 1,84 g/ml), H SO (freshly prepared).
2 4
Dilute concentrated sulfuric acid (H SO ), ρ ≈ 1,84 g/ml, w(H SO ) ≈ 98 % 1 + 1 by carefully adding the
2 4 2 4
concentrated acid to an equal volume of water and mix.
WARNING — Adding the concentrated acid to the water can give violent reactions because of an
exothermic reaction.
5.2.6 Sodium hydroxide solution (ρ ≈ 0,40 g/ml), NaOH.
5.2.7 Formaldehyde solution (formalin), CH O, ϕ(CH O) = 37 % to 40 % (freshly prepared),
2 2
WARNING — Beware of formaldehyde vapours. Do not store large numbers of samples in
small work areas.
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ISO 5667-3:2012(E)
5.2.8 Disodium salt of ethylenediaminetetraacetic acid (EDTA) (ρ ≈ 0,025 g/ml),
C H N Na O ⋅2H O, w(C H N Na O ⋅2H O) > 99 %.
10 14 2 2 8 2 10 14 2 2 8 2
Dissolve 25 g EDTA in 1 000 ml of water.
5.2.9 Ethanol C H OH, ϕ(C H OH) = 96 %.
2 5 2 5
5.2.10 Alkaline Lugol’s solution, 100 g potassium iodide (5.1.6), 50 g iodine (5.1.7), and 250 g sodium
acetate (5.1.8) in 1 000 ml water to pH 10.
5.2.11 Acidic Lugol’s solution, 100 g potassium iodide (5.1.6), 50 g iodine (5.1.7) and 100 ml glacial
acetic acid (5.2.17) in 1 000 ml water to pH 2.
5.2.12 Neutralized formaldehyde solution, formaldehyde solution (5.2.7) neutralized with sodium
tetraborate (5.1.4) or hexamethylenetetramine (5.1.5). Formalin solution at 100 g/l gives a final solution
of ϕ(CH O) = 3,7 % to 4,0 %.
2
WARNING — Beware of formaldehyde vapours. Do not store large numbers of samples in
small work areas.
5.2.13 Ethanol preservative solution.
Ethanol (5.2.9), formaldehyde solution (5.2.7) and glycerol (5.2.18) (100 + 2 + 1 parts by volume,
respectively).
5.2.14 Sodium hypochlorite NaOCl, w(NaOCl) = 10 %. Dissolve 100 g sodium hypochlorite (NaOCl) in
1 000 ml of water.
5.2.15 Potassium iodate KIO , w(KIO ) = 10 %. Dissolve 100 g potassium iodate (KIO ) in 1 000 ml of water.
3 3 3
5.2.16 Methanoic acid (formic acid) CH O , ϕ(CH O ) > 98 %.
2 2 2 2
5.2.17 Glacial acetic acid C H O , w(C H O ) > 99 %.
2 4 2 2 4 2
5.2.18 Glycerol (glycerin, glycerine) C H (OH) .
3 5 3
5.3 Materials
5.3.1 Container and cap, types as specified in Tables A.1 to A.3.
5.3.2 Filter, pore size 0,40 µm to 0,45 µm, unless a different filter size is specified in the analytical
International Standard.
6 Containers
6.1 Container selection and preparation
The choice of sample container (5.3.1) is of major importance and ISO 5667-1 provides some guidance
on this subject.
Details of the type of container used for the collection and storage of samples are given in Tables A.1 to
A.3. The same considerations given to this selection of suitable container material shall also be given to
the selection of cap liner materials.
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ISO 5667-3:2012(E)
Sample containers shall be made of a material appropriate for preserving the natural properties of both
the sample and the expected range of contaminants. Suitable types of containers for each analyte to be
measured are given in Tables A.1 to A.3.
NOTE For very low concentrations of metals, containers prescribed can be different from those used for
higher concentrations. Details can be found in Table A.1 or in the analytical International Standards.
If the samples are to be frozen, suitable containers, such as polyethylene (PE) or polytetrafluoroethylene
(PTFE), shall be used to prevent breakage.
The use of disposables is preferred. Some manufacturers supply containers with a certificate of
cleanliness. If such a certificate of cleanliness is supplied, it is not necessary to clean or rinse the
containers before use.
6.2 Filtration on site
Filtration on site is required in some cases.
— Groundwaters shall be filtered on site if dissolved metals need to be analysed.
— Waters shall be filtered (5.3.2) on site, if this is required according to Annex A. Unless specified
otherwise, a filter pore size 0,40 µm to 0,45 µm shall be used.
If immediate filtration on site is impossible, then the reason and the time between sampling and filtration
shall be added to the test report.
6.3 Filling the container
The container (5.3.1) shall be filled completely unless prescribed differently in Tables A.1 to A.3 or the
analytical International Standard used. If the samples are to be frozen as part of their preservation,
sample containers shall not be completely filled. This is in order to prevent breakage which may arise
from expansion of ice during the freezing and thawing process.
If no preservatives are present in the bottle, then prerinsing the bottle may be advisable. Guidance on
prerinsing can be found in ISO 5667-14.
7 Sample handling and preservation
7.1 Sample handling and preservation for physical and chemical examination
Waters, particularly fresh waters, waste waters and groundwaters, are susceptible to changes as a result
of physical, chemical or biological reactions which may take place between the time of sampling and the
commencement of analysis. The nature and rate of these reactions are often such that, if precautions are
not taken during sampling, transport and storage (for specific analytes), the concentrations determined
are different to those existing at the time of sampling.
The extent of these changes is dependent on the chemical and biological nature of the sample, its
temperature, its exposure to light, the type of the container in which it is placed, the time between
sampling and analysis, and the conditions to which it is subjected, e.g. agitation during transport.
Further specific causes of variation are listed in a) to f).
a) The presence of bacteria, algae and other organisms can consume certain constituents of the samples.
These organisms can also modify the nature of the constituents to produce new constituents. This
biological activity affects, for example, the concentrations of dissolved oxygen, carbon dioxide,
compounds of nitrogen, phosphorus and, sometimes, silicon.
b) Certain compounds can be oxidized either by dissolved oxygen present in the samples, or by
atmospheric oxygen [e.g. organic compounds, Fe(II) and sulfides].
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ISO 5667-3:2012(E)
c) Certain substances can precipitate out of solution, e.g. calcium carbonate, metals, and metallic
compounds such as Al(OH) , or can be lost to the vapour phase (e.g. oxygen, cyanides, and mercury).
3
d) Absorption of carbon dioxide from air can modify pH, conductivity, and the concentration of
dissolved carbon dioxide. Passage of compounds like ammonia and silicon fluoride through some
types of plastics may also affect pH or conductivity.
e) Dissolved metals or metals in a colloidal state, as well as certain organic compounds, can be
irreversibly adsorbed on to the surface of the containers or solid materials in the samples.
f) Polymerized products can depolymerize, and conversely, simple compounds can polymerize.
Changes to particular constituents vary both in degree and rate, not only as a function of the type of
water, but also, for the same water type, as a function of seasonal conditions.
These changes are often sufficiently rapid to modify the sample considerably in a short time. In all cases,
it is essential to take precautions to minimize these reactions and, in the case of many analytes, to
analyse the sample with a minimum of delay. If the required precaution for changes is filtration on site,
then a filter (5.3.2) shall be used.
Details of the sample preservation are given in Table A.1.
7.2 Sample handling and preservation for biological examination
The handling of samples for biological examination is different from that for samples requiring chemical
analysis. The addition of chemicals to the sample for biological examination can be used for either fixation
and/or preservation of the sample. The term “fixation” is defined as the protection of morphological
structures, while the term “preservation” is defined as the protection of organic matter from biochemical
or chemical degradation. Preservatives, by definition, are toxic, and the addition of preservatives may
lead to the death of living organisms. Prior to death, irritation may cause the most delicate organisms,
which do not have strong cell walls, to collapse before fixation is complete. To minimize this effect, it is
important that the fixation agent enter the cell quickly.
IMPORTANT Acidic Lugol’s solutions (5.2.11) can lead to the loss of structures in organisms or also
lead to the loss of small organisms (e.g. some flagellates); in this case, use an alkaline Lugol’s solution
(5.2.10), e.g. during the summer, when the appearance of silico-flagellates is frequently observed.
The fixing and/or preservation of samples for biological examination shall meet the following criteria:
a) the effect of the fixative, and/or preservative, on the loss of the organism shall be known beforehand;
b) the fixative or preservative shall effectively prevent the biological degradation of organic matter at
least during the storage period of the samples;
c) the fixative, and/or preservative, shall enable the biological analyte (e.g. organisms or taxonomical
groups) to be assessed during the storage period of the samples.
Details of the preservation of samples are given in Table A.2.
7.3 Sample handling and preservation for radiochemical analysis
WARNING — Radioprotection such as shielding may be necessary, depending on the activity
of the sample.
There is little difference between the handling of samples for radiochemical analysis and the handling
of samples for physicochemical analysis.
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ISO 5667-3:2012(E)
The delay between sampling and measurement has to be consistent with the radioactive half-life of
the radionuclides of interest. The conditions to be taken for adequate storage are independent of the
radioactive half-life, but identical to those required for the corresponding stable isotope.
NOTE Cooling radiological samples is primarily used to prevent algal growth and biological spoilage. It is
not a necessary preservation step for radiochemical analyses. These samples are often combined with those for
physical, chemical or biological analysis.
8 Sample transport
Cooling or freezing procedures shall be applied to samples to increase the time period available for
transport and storage and if required by Tables A.1 to A.3. When transport takes place, the sampling
plan (e.g. ISO 5667-1) shall consider:
— the time between sampling and start of transport;
— transport time;
— starting time of analysis in the laboratory.
This sum of these three periods is limited to the maximum storage times according to Tables A.1 to A.3.
If the maximum storage time cannot be met, then the sampling plan shall be reformulated to allow these
requirements to be accommodated.
A cooling temperature of the device during transport of (5 ± 3) °C has been found suitable for many
applications. Cooling and freezing procedures applied shall be in line with instructions from the
analytical laboratory. Freezing especially requires detailed control of the freezing and thawing process
in order to return the sample to its initial equilibrium after thawing.
Containers holding samples shall be protected and sealed during transport in such a way that the samples
do not deteriorate or lose any part of their content. Container packaging shall protect the containers
from possible external contamination, particularly near the opening, and should not itself be a source
of contamination.
Glass containers shall be protected from potential breakage during transport by appropriate packaging.
Samples shall be transported as soon as possible after sampling and with cooling if necessary according
to Tables A.1 to A.3.
Laboratory samples for dispatch or transport by third parties and preserved laboratory samples should
be sealed in such manner that the integrity of the sample can be maintained.
Samples required for (potential) regulatory investigations should be sealed to a level that meets the
requirements of the authorities or other organization(s) concerned with the transport of the sample.
During transportation samples shall be stored in a cooling device capable of maintaining a temperature
of (5 ± 3) °C. For proper evaluation of the conditions during transport a device capable of recording the
(maximum) temperature of the air surrounding the sample may be used.
NOTE Devices capable of logging of the air temperature during the transportation are available, but their use
and adequate calibration can be costly.
9 Identification of samples
Container labels shoul
...
DRAFT INTERNATIONAL STANDARD ISO/DIS 5667-3
ISO/TC 147/SC 6 Secretariat: BSI
Voting begins on Voting terminates on
2010-12-16 2011-05-16
INTERNATIONAL ORGANIZATION FOR STANDARDIZATION • МЕЖДУНАРОДНАЯ ОРГАНИЗАЦИЯ ПО СТАНДАРТИЗАЦИИ • ORGANISATION INTERNATIONALE DE NORMALISATION
Water quality — Sampling —
Part 3:
Preservation and handling of water samples
Qualité de l'eau — Échantillonnage —
Partie 3: Conservation et manipulation des échantillons d'eau
[Revision of third edition (ISO 5667-3:2003)]
ICS 13.060.45
ISO/CEN PARALLEL PROCESSING
This draft has been developed within the International Organization for Standardization (ISO), and
processed under the ISO-lead mode of collaboration as defined in the Vienna Agreement.
This draft is hereby submitted to the ISO member bodies and to the CEN member bodies for a parallel
five-month enquiry.
Should this draft be accepted, a final draft, established on the basis of comments received, will be
submitted to a parallel two-month approval vote in ISO and formal vote in CEN.
In accordance with the provisions of Council Resolution 15/1993 this document is circulated in
the English language only.
Conformément aux dispositions de la Résolution du Conseil 15/1993, ce document est distribué
en version anglaise seulement.
To expedite distribution, this document is circulated as received from the committee
secretariat. ISO Central Secretariat work of editing and text composition will be undertaken at
publication stage.
Pour accélérer la distribution, le présent document est distribué tel qu'il est parvenu du
secrétariat du comité. Le travail de rédaction et de composition de texte sera effectué au
Secrétariat central de l'ISO au stade de publication.
THIS DOCUMENT IS A DRAFT CIRCULATED FOR COMMENT AND APPROVAL. IT IS THEREFORE SUBJECT TO CHANGE AND MAY NOT BE
REFERRED TO AS AN INTERNATIONAL STANDARD UNTIL PUBLISHED AS SUCH.
IN ADDITION TO THEIR EVALUATION AS BEING ACCEPTABLE FOR INDUSTRIAL, TECHNOLOGICAL, COMMERCIAL AND USER PURPOSES,
DRAFT INTERNATIONAL STANDARDS MAY ON OCCASION HAVE TO BE CONSIDERED IN THE LIGHT OF THEIR POTENTIAL TO BECOME
STANDARDS TO WHICH REFERENCE MAY BE MADE IN NATIONAL REGULATIONS.
RECIPIENTS OF THIS DRAFT ARE INVITED TO SUBMIT, WITH THEIR COMMENTS, NOTIFICATION OF ANY RELEVANT PATENT RIGHTS OF WHICH
THEY ARE AWARE AND TO PROVIDE SUPPORTING DOCUMENTATION.
© International Organization for Standardization, 2010
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ISO/DIS 5667-3
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ii © ISO 2010 – All rights reserved
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ISO/DIS 5667-3
Contents Page
1 Scope .1
2 Normative references.1
3 Terms and definitions .1
4 Sampling.2
5 Handling and preservation of samples.2
6 Sample transport.7
7 Sample reception .7
8 Identification of samples.7
9 Sample storage .8
Annex A (informative) Container preparation . 35
Annex B (informative) Preservation techniques for use with multiple analytes. 37
Annex C (informative) Protocol as used in Dutch validation studies. 42
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ISO/DIS 5667-3
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the
International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 5667-3 was prepared by Technical Committee ISO/TC 147, Water Quality, Subcommittee SC 6,
Sampling.
This fourth edition cancels and replaces the third edition (ISO 5667-3:2003), which has been technically
revised.
ISO 5667 consists of the following parts, under the general title Water Quality — Sampling:
¾ Part 1: Guidance on the design of sampling programmes and techniques
¾ Part 3: Preservation and handling of water sample
¾ Part 4: Guidance on sampling from lakes, natural and man-made
¾ Part 5: Guidance on sampling of drinking water and water used for food and beverage processing
¾ Part 6: Guidance on sampling of rivers and streams
¾ Part 7: Guidance on sampling of water and steam in boiler plants
¾ Part 8: Guidance on the sampling of wet deposition
¾ Part 9: Guidance on sampling from marine waters
¾ Part 10: Guidance on sampling of waste waters
¾ Part 11: Guidance on sampling of groundwaters
¾ Part 13: Guidance on sampling of sludges from sewage and water-treatment works
¾ Part 14: Guidance on quality assurance of environmental water-sampling and handling
¾ Part 15: Guidance on preservation and handling of sludge and sediment samples
¾ Part 16: Guidance on biotesting of samples
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ISO/DIS 5667-3
¾ Part 18: Guidance on sampling of groundwater at contaminated sites
¾ Part 19: Guidance on sediment sampling in marine areas
¾ Part 20: Guidance on the use of sampling data for decision making - Compliance with thresholds and
classification systems
¾ Part 21: Guidance on sampling of drinking water distributed by non-continuous, non-conventional means
¾ Part 22: Guidance on design and installation of groundwater sample points
The following part is in preparation:
¾ Part 23: Determination of significant pollutants in surface waters using passive sampling
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ISO/DIS 5667-3
Introduction
This part of ISO 5667 is intended to be used in conjunction with ISO 5667-1, which deals with the design of
sampling programmes and sampling techniques.
Where possible this standard has been brought into line with existing, current standards. Where new research
or validation results have provided new insights, the latest knowledge has been used.
Guidance on validation protocols can be found in ISO Guide 34
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DRAFT INTERNATIONAL STANDARD ISO/DIS 5667-3
Water quality — Sampling —
Part 3:
Preservation and handling of water samples
1 Scope
This part of ISO 5667 establishes general principles for sampling, preservation, handling, transport and
storage of all water samples including those for biological analyses, but not those intended for microbiological
analysis, ecotoxicological assays and passive sampling as described in the scope of ISO 5667-23.
This standard is particularly appropriate when spot or composite samples cannot be analyzed on site and
have to be transported to a laboratory for analysis.
The preservation techniques specified in this International Standard are applicable if there are no
contradictory requirements concerning the preservation of samples in the analytical method intended to be
carried out after the completion of the procedures described. Differing preservation requirements of analytical
methods may be tailored to the particular requirements of the specific analytical method. Contradictory
requirements shall be the result of changes in analytical techniques and standards The reason for particular
deviation shall be noted in the most recent analytical method standard.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 5667-1, Water quality — Sampling — Part 1: Guidance on the design of sampling programmes
ISO 15913, Water quality — Determination of selected phenoxyalkanoic herbicides, including bentazones and
hydroxybenzonitriles by gas chromatography and mass spectrometry after solid phase extraction and
derivatization
ISO 19458, Water quality — Sampling for microbiological analysis
3 Terms and definitions
For the purposes of this document, the terms and definitions given in the ISO 6107-series and the following
apply.
3.1
sample preservation
any procedure used to stabilize a sample in such a way that the properties under examination are maintained
stable from the collection step until preparation for analysis
[ISO 11074:2005, 4.4.20]
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ISO/DIS 5667-3
NOTE Different analytes may require several samples from the same source that are stabilized by different
procedures .
3.2
sample storage
process, and the result, of keeping a sample available under predefined conditions for a (usually) specified
time interval between collection and further treatment of a sample
[ISO 11074:2005, 4.4.22]
NOTE Specified time is the maximum time interval.
3.3
storage time
period of time between filling of the sample container and further treatment of the sample in the laboratory, if
stored under predefined conditions. Sampling finishes as soon as the sample container has been filled with
sample. Storage time ends when the sample is taken by the analyst to start sample preparation prior to
analysis
NOTE Further treatment, is for most of the analytes, a solvent extraction or acid destruction. The initial steps of
sample preparation, may be steps complementary to the storage conditions for the securing of analyte concentrations .
4 Sampling
If there is a need to take samples this will be done according a sampling programme. The first step is to
design a sampling programme. Guidance on this topic is given in ISO 5667-1.
Depending on the sample type and matrix, guidance can be found in the different ISO 5667-documents and
ISO 19458.
The process of preservation and handling of water samples consists of several steps. During this process, the
responsibility for the samples might change. To ensure the integrity of the samples, it is vital that all steps
involving the sample be documented.
5 Handling and preservation of samples
5.1 Reagents and materials
WARNING — Certain preservatives (e.g. acids, alkalis, formaldehyde) need to be used with caution.
Sampling personnel should be warned of potential dangers, and appropriate safety procedures should
be followed.
The following reagents are used for the preservation of samples and shall only be prepared according to
individual sampling requirements. Unless otherwise specified, all reagents used shall be of at least analytical
reagent grade and water shall be of at least ISO 3696 Grade 2 purity. Acids referred to in this part of ISO 5667
are commercially available “concentrated” acids.
All reagents shall be labelled with a “shelf life”. The “shelf life” represents the period for which the reagent is
suitable for use, if stored correctly. This “shelf life” shall not be exceeded. Any reagents that are not
completely used by the expiry of the “shelf life” date shall be discarded.
Check the reagent dispensers periodically and discard any reagent where dispensers are shown to be
unsuitable.
Between field trips, reagents shall be stored in clean, secure cabinets in order to prevent contamination.
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ISO/DIS 5667-3
Each sample shall be labelled accordingly, after the addition of the preservative. Otherwise, there may be no
visible indication as to which samples have been preserved, and which have not.
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ISO/DIS 5667-3
5.1.1 Solids
.
5.1.1.1 Sodium thiosulfate pentahydrate, Na S O 5H O
2 2 3 2
5.1.1.2 Ascorbic acid, C H O
6 8 6
5.1.1.3 Sodium hydroxide, NaOH
.
5.1.1.4 Sodium tetraborate decahydrate, Na B O 10H O
2 4 7 2
5.1.1.5 Hexamethylenetetramine (hexamine, urotropine), C H N
6 12 4
5.1.1.6 Potassium iodide, KI
Iodine, I
5.1.1.7 2
5.1.1.8 Sodium actetate, C H NaO
2 3 2
5.1.2 Solutions
5.1.2.1 Zinc acetate solution (r = 0,10 g/ml), C H O Zn
4 6 4
5.1.2.2 Orthophosphoric acid (r = 1,7 g/ml), H PO
3 4
5.1.2.3 Hydrochloric acid (r = 19 g/ml), HCl
5.1.2.4 Nitric acid (r = 1,42 g/ml), HNO
3
5.1.2.5 Sulfuric acid (8 mol/l), H SO
2 4
5.1.2.6 Sodium hydroxide solution (r = 0,40 g/ml), NaOH
5.1.2.7 Formaldehyde solution (volume fraction of 37 %) (Formalin), CH O
2
WARNING — Beware of formaldehyde vapours. Do not store large numbers of samples in small work
areas.
5.1.2.8 Aqueous solution of disodium salt of ethylenediaminetetraacetic (EDTA) (r = 0,025 g/ml),
C H N Na O ×2H O
10 14 2 2 8 2
5.1.2.9 Ethanol (volume fraction of 96 %)
5.1.2.10 Alkaline Lugol solution, 100g Potassium iodide (5.1.1.6), 50 g Iodine (5.1.1.7) and 250 g Sodium
acetate (5.1.1.8) in 1 000 ml water to pH 10
5.1.2.11 Acid Lugol solution, 100g Potassium iodide (5.1.1.6), 50 g Iodine (5.1.1.7) and 100 ml acetic acid
glacial (5.1.2.17) in 1 000 ml water, to pH 2
5.1.2.12 Formaldehyde Solution, 37 % formaldehyde neutralized with sodium tetraborate or
hexamethylene-tetramine (100 g/l formalin solution) to give a final solution of 3,7 % formaldehyde
5.1.2.13 Ethanol preservative solution, at least 70 % by volume fraction ethanol, 37 % by volume fraction
and glycerol (in the proportions 100:2:1 respectively).
4 © ISO 2010 – All rights reserved
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ISO/DIS 5667-3
5.1.2.14 Sodium hypochlorite (mass fraction of 10 %), NaOCl
Potassium iodate (mass fraction of 10 %), KIO
5.1.2.15 3
Methanoic acid (formic acid) (volume fraction of > 98%) CH O
5.1.2.16 2 2
5.1.2.17 Acetic acid glacial C H O
2 4 2
5.1.3 Materials
5.1.3.1 Container - Type and volumes specified in Table 1-3
5.1.3.2 Filter – pore size 0.40 - 0.45 µm
5.2 Container selection and preparation
The choice of sample container (5.1.3.1) is of major importance and ISO 5667-1 provides some guidance on
this subject.
Details of the type of container used for the collection and storage of samples are given in Tables 1-3. The
same considerations given to this selection of suitable container material shall also be given to the selection of
cap-liner materials.
Sample containers shall be made of a material appropriate for preserving the natural properties of both the
sample and the expected range of contaminants. Suitable types of containers for each analyte to be
measured are given in Tables 1-3.
If the samples are to be frozen, suitable containers, such as polyethylene or polytetrafluoroethylene (PTFE),
shall be used to prevent breakage.
If disposables are available, these shall be used. Some manufactures will supply containers with a certificate
of cleanliness. Such containers shall never be cleaned or rinsed, provided the manufacturer supplies the
containers with caps attached.
All preparation procedures shall be validated to ensure positive or negative interferences do not occur. As a
minimum, this shall include the analysis of blanks and/or samples containing known levels of relevant analytes.
5.3 Filling the container
The container (5.1.3.1) shall be filled completely unless prescribed differently in the Tables 1-3. If the samples
are to be frozen as part of their preservation, sample containers shall not be completely filled, to prevent
breakage.
5.4 Handling and preservation of samples for physical and chemical examination
Waters, particularly fresh waters, waste waters and groundwaters, are susceptible to changes as a result of
physical, chemical or biological reactions which may take place between the time of sampling and the
commencement of analysis. The nature and rate of these reactions are often such that, if precautions are not
taken during sampling, transport and storage (for specific analytes), the concentrations determined shall be
different to those existing at the time of sampling.
The extent of these changes is dependent on the chemical and biological nature of the sample, its
temperature, its exposure to light, the nature of the container in which it is placed, the time between sampling
and analysis, and the conditions to which it is subjected, e.g. agitation during transport. Further specific
causes of variation are as follows:
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ISO/DIS 5667-3
a) The presence of bacteria, algae and other organisms can consume certain constituents of the samples.
These organisms can also modify the nature of the constituents to produce new constituents. This
biological activity affects, for example, the concentrations of dissolved oxygen, carbon dioxide,
compounds of nitrogen, phosphorus and, sometimes, silicon.
b) Certain compounds can be oxidized either by dissolved oxygen present in the samples, or by
atmospheric oxygen (e.g. organic compounds, Fe (II) and sulfides).
c) Certain substances can precipitate out of solution [for example calcium carbonate, metals and metallic
compounds such as Al(OH) , or can be lost to the vapour phase (for example oxygen, cyanides and
3
mercury).
d) Absorption of carbon dioxide from air can modify pH, conductivity and the concentration of dissolved
carbon dioxide. Passage of compounds like ammonia and silicon fluoride through some types of plastics
may also affect pH or conductivity.
e) Dissolved metals or metals in a colloidal state, as well as certain organic compounds can be irreversibly
adsorbed onto the surface of the containers or solid materials in the samples.
f) Polymerized products can depolymerize, and conversely, simple compounds can polymerize.
Changes to particular constituents vary both in degree and rate, not only as a function of the type of water, but
also, for the same water type, as a function of seasonal conditions.
lt should be emphasized that these changes are often sufficiently rapid to modify the sample considerably in a
short time. In all cases, it is essential to take precautions to minimize these reactions and, in the case of many
analytes, to analyze the sample with a minimum of delay. If the required precaution for changes is filtration on
site, then a filter (5.1.3.2.) shall be used.
5.5 Handling and preservation of samples for biological examination
The handling of samples for biological examination is different from that for samples requiring chemical
analysis. The addition of chemicals to the sample for biological examination is used for either fixation and/or
preservation of the sample. The term “fixation” is used to describe the protection of morphological structures,
while the term “preservation” is used for the protection of organic matter from biochemical or chemical
degradation. Preservatives, by definition, are toxic, and the addition of preservatives may lead to the death of
living organisms. Prior to death, irritation may cause the most delicate organisms, which do not have strong
cell walls, to collapse before fixation is complete. To minimize this effect, it is important that the fixation agent
enters the cell quickly. Some preservatives, for instance, acid solutions of Lugol (5.1.2.11), may lead to the
loss of some taxonomical groups of organisms, which can be a problem during certain parts of the year in
certain areas. In that case an additional preservative, such as alkaline solutions of Lugol (5.1.2.10), shall be
added, for example, in the summer period when the appearance of silico-flagellates may be frequently
observed.
The fixing and/or preservation of samples for biological examination shall meet the following criteria:
a) the effect of the fixative, and/or preservative, on the loss of the organism shall be known beforehand;
b) the fixative or preservative shall effectively prevent the biological degradation of organic matter at least
during the storage period of the samples;
c) the fixative, and/or preservative, shall enable the taxonomical groups of organisms to be adequately
studied during the storage period of the samples.
5.6 Handling and preservation of samples for radiochemical analysis
WARNING — Safety precautions and shielding depend on the activity of the sample.
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ISO/DIS 5667-3
There is little difference between the handling of samples for radiochemical analysis and the handling of
samples for physico-chemical analysis. Safety precautions depend on the nature of the radioactivity of the
sample. The preservation techniques for these samples depend on the type of emitter and the half-life of the
radionuclide of interest.
6 Sample transport
Cooling or freezing procedures shall be applied to samples to increase the time period available for transport
and storage and if required by tables 1-3. When transport takes place the sampling (plan) shall consider the
total time between sampling and start of analysis in the laboratory, the storage time and the degree of
representativeness of the sample which may be limited by maximum storage times according to table1-3 or
cost or convenience.
o
A cooling temperature during transport of (5 ± 3) C has been found suitable for many applications. Cooling
and freezing procedures applied shall be in line with instructions from the analytical laboratory. Freezing
especially requires detailed control of the freezing and thawing process in order to return the sample to its
initial equilibrium after thawing.
NOTE Cool boxes and freezer packs are capable of at least maintaining the temperature of the sample during
sampling during transport.
Containers holding samples shall be protected and sealed during transport in such a way that the samples do
not deteriorate or lose any part of their content. Container packaging shall protect the containers from possible
external contamination, particularly near the opening, and should not itself be a source of contamination.
Glass containers shall be protected from potential breakage during transport by appropriate packaging.
Samples shall be transported as soon as possible after sampling and with cooling if necessary according to
Table 1-3.
Laboratory samples for dispatch or transport by third parties and preserved laboratory samples shall be
sealed in such manner that the integrity of the sample can be maintained.
Samples required for (potential) regulatory investigations shall be sealed to a level that meets the
requirements of the authorities or other organization(s) concerned with the transport of the sample.
During transportation samples shall be stored in a cooling device capable of maintaining a temperature
o
between (5 ± 3) C. For proper evaluation of the conditions during transport a device capable of recording the
(maximum) temperature of the air surrounding the sample can be used.
NOTE Devices, capable of logging of the air temperature during the transportation are available but the use and
adequate calibration may be costly.
7 Sample reception
Laboratory staff shall receive and check relevant information on preservation and transport conditions of the
sample.
All information regarding sample manipulation, handling, and storage shall be included in a sampling report.
In all cases, and especially when a “chain of custody” process needs to be established, the number of sample
containers received in the laboratory shall be verified against the number of sample containers submitted.
8 Identification of samples
Container labels should withstand wetting, drying and freezing without detaching or becoming illegible. The
labelling system shall be waterproof to allow use in the field.
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ISO/DIS 5667-3
The exact information given in the sampling report and on the sample labels will depend on the objectives of
the particular measurement programme. In all cases, an indelible label shall be secured to the sample
container.
For each sample, at least the following information shall be available:
A unique identifier, traceable to
¾ Date, time and location of sampling;
¾ Sample number;
¾ Description and disposition of sample;
¾ Name of sampling personnel;
¾ Details of preservation, or fixation used;
¾ Details of sample storage used;
¾ Any information regarding integrity and manipulation of the sample;
¾ All other information as necessary.
A unique identifier, traceable to sample date, location and sample number shall be on the label of the sample
container.
All other information is additional and can be found in the sample report.
9 Sample storage
The storage duration of the water samples within the laboratory is specific to the analyte(s) to be analyzed.
Samples shall be stored no longer than the maximum storage duration times given in Tables 1-3.
The cooling conditions within the laboratory shall be between (3 ± 2) °C. These are different from the cooling
conditions during transport (5 ± 3) °C.
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ISO/DIS 5667-3
Table 1 — Techniques for the preservation of samples —
Physico-chemical and chemical analysis
Typical volume Maximum Validated or
Specification of matrices Preservation and storage
a
Analyte to be studied Type of container (ml) and filling storage best Comments
or (individual) compounds conditions
b
duration practice
technique
For samples high in dissolved gases,
analyze preferably on site.
Acidity and alkalinity P or G 500 Cool to between (3 ± 2) °C 14 days Validated
Reduction and oxidation during storage
can change the sample.
Acidify to pH 1 to 2 with
HNO (5.1.2.4.).
3
e
Adsorbable organic
Cool to between (3 ± 2) °C.
e
P or G 1 000 5 days Best practice
halides
Keep samples stored in the
(AOX)
dark or use dark-coloured
bottles.
P 1 000 Freeze to < – 18 °C. 1 month Best practice
Filter ground water on site.
Alumini
...
FINAL
INTERNATIONAL ISO/FDIS
DRAFT
STANDARD 5667-3
ISO/TC 147/SC 6
Water quality — Sampling —
Secretariat: BSI
Voting begins on:
Part 3:
2012-09-06
Preservation and handling of water
Voting terminates on:
samples
2012-11-06
Qualité de l’eau — Ėchantillonnage —
Partie 3: Conservation et la manipulation des échantillions d’eau
Please see the administrative notes on page iii
RECIPIENTS OF THIS DRAFT ARE INVITED TO
SUBMIT, WITH THEIR COMMENTS, NOTIFICATION
OF ANY RELEVANT PATENT RIGHTS OF WHICH
THEY ARE AWARE AND TO PROVIDE SUPPOR TING
DOCUMENTATION.
IN ADDITION TO THEIR EVALUATION AS
Reference number
BEING ACCEPTABLE FOR INDUSTRIAL, TECHNO-
ISO/FDIS 5667-3:2012(E)
LOGICAL, COMMERCIAL AND USER PURPOSES,
DRAFT INTERNATIONAL STANDARDS MAY ON
OCCASION HAVE TO BE CONSIDERED IN THE
LIGHT OF THEIR POTENTIAL TO BECOME STAN-
DARDS TO WHICH REFERENCE MAY BE MADE IN
©
NATIONAL REGULATIONS. ISO 2012
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ISO/FDIS 5667-3:2012(E)
Copyright notice
This ISO document is a Draft International Standard and is copyright-protected by ISO. Except as
permitted under the applicable laws of the user’s country, neither this ISO draft nor any extract
from it may be reproduced, stored in a retrieval system or transmitted in any form or by any means,
electronic, photocopying, recording or otherwise, without prior written permission being secured.
Requests for permission to reproduce should be addressed to either ISO at the address below or ISO’s
member body in the country of the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Reproduction may be subject to royalty payments or a licensing agreement.
Violators may be prosecuted.
ii © ISO 2012 – All rights reserved
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ISO/FDIS 5667-3:2012(E)
ISO/CEN PARALLEL PROCESSING
This final draft has been developed within the International Organization for Standardization (ISO), and pro-
cessed under the ISO-lead mode of collaboration as defined in the Vienna Agreement. The final draft was
established on the basis of comments received during a parallel enquiry on the draft.
This final draft is hereby submitted to the ISO member bodies and to the CEN member bodies for a parallel
two-month approval vote in ISO and formal vote in CEN.
Positive votes shall not be accompanied by comments.
Negative votes shall be accompanied by the relevant technical reasons.
© ISO 2012 – All rights reserved iii
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ISO/FDIS 5667-3:2012(E)
Contents Page
Foreword .v
Introduction .vii
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Sampling and chain of custody . 2
5 Reagents and materials . 2
5.1 Solids . 3
5.2 Solutions . 3
5.3 Materials . 4
6 Containers . 4
6.1 Container selection and preparation . 4
6.2 Filtration on site . 5
6.3 Filling the container . 5
7 Sample handling and preservation . 5
7.1 Sample handling and preservation for physical and chemical examination . 5
7.2 Sample handling and preservation for biological examination . 6
7.3 Sample handling and preservation for radiochemical analysis . 6
8 Sample transport . 7
9 Identification of samples . 7
10 Sample reception . 8
11 Sample storage . 8
Annex A (informative) Techniques for sample preservation . 9
Annex B (informative) Container preparation .35
Annex C (informative) Protocol as used in Dutch validation studies .36
Bibliography .38
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ISO/FDIS 5667-3:2012(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International
Standards adopted by the technical committees are circulated to the member bodies for voting.
Publication as an International Standard requires approval by at least 75 % of the member bodies
casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 5667-3 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 6,
Sampling (general methods).
This fourth edition cancels and replaces the third edition (ISO 5667-3:2003), which has been
technically revised.
ISO 5667 consists of the following parts, under the general title Water quality — Sampling:
— Part 1: Guidance on the design of sampling programmes and sampling techniques
— Part 3: Preservation and handling of water samples
— Part 4: Guidance on sampling from lakes, natural and man-made
— Part 5: Guidance on sampling of drinking water from treatment works and piped distribution systems
— Part 6: Guidance on sampling of rivers and streams
— Part 7: Guidance on sampling of water and steam in boiler plants
— Part 8: Guidance on the sampling of wet deposition
— Part 9: Guidance on sampling from marine waters
— Part 10: Guidance on sampling of waste waters
— Part 11: Guidance on sampling of groundwaters
— Part 12: Guidance on sampling of bottom sediments
— Part 13: Guidance on sampling of sludges
— Part 14: Guidance on quality assurance of environmental water-sampling and handling
— Part 15: Guidance on the preservation and handling of sludge and sediment samples
— Part 16: Guidance on biotesting of samples
— Part 17: Guidance on sampling of bulk suspended solids
— Part 19: Guidance on sampling of marine sediments
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ISO/FDIS 5667-3:2012(E)
— Part 20: Guidance on the use of sampling data for decision making — Compliance with thresholds and
classification systems
— Part 21: Guidance on sampling of drinking water distributed by tankers or means other than
distribution pipes
— Part 22: Guidance on the design and installation of groundwater monitoring points
— Part 23: Guidance on passive sampling in surface waters
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ISO/FDIS 5667-3:2012(E)
Introduction
This part of ISO 5667 is intended to be used in conjunction with ISO 5667-1, which deals with the design
of sampling programmes and sampling techniques.
Where possible this part of ISO 5667 has been brought into line with current standards. Where new
research or validation results have provided new insights, the latest knowledge has been used.
[63]
Guidance on validation protocols can be found in ISO Guide 34.
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FINAL DRAFT INTERNATIONAL STANDARD ISO/FDIS 5667-3:2012(E)
Water quality — Sampling —
Part 3:
Preservation and handling of water samples
NOTICE — This part of ISO 5667 and the analytical International Standards listed in Annex A
are complementary. Where no analytical International Standard is applicable, the technique(s)
described in Tables A.1 to A.3 take(s) normative status.
When new or revised analytical standards are developed with storage times or preservative
techniques differing from those in Tables A.1 to A.3, then the storage times or preservative
techniques should be validated and presented to ISO/TC 147/SC 6/WG 3 for incorporation into
the next revision of this part of ISO 5667.
1 Scope
This part of ISO 5667 establishes general requirements for sampling, preservation, handling, transport
and storage of all water samples including those for biological analyses. It is not applicable to water
samples intended for microbiological analyses as specified in ISO 19458, ecotoxicological assays,
biological assays, and passive sampling as specified in the scope of ISO 5667-23.
This part of ISO 5667 is particularly appropriate when spot or composite samples cannot be analysed on
site and have to be transported to a laboratory for analysis.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 5667 (all parts), Water quality — Sampling
ISO 19458, Water quality — Sampling for microbiological analysis
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
integrity
property that the parameter(s) of interest, information or content of the sample container has not been
altered or lost in an unauthorized manner or subject to loss of representativeness
3.2
sample preservation
any procedure used to stabilize a sample in such a way that the properties under examination are
maintained stable from the collection step until preparation for analysis
[29]
[ISO 11074:2005, 4.4.20]
NOTE Different analytes may require several samples from the same source that are stabilized by
different procedures.
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ISO/FDIS 5667-3:2012(E)
3.3
sample storage
process, and the result, of keeping a sample available under predefined conditions for a (usually)
specified time interval between collection and further treatment of a sample
[29]
NOTE 1 Adapted from ISO 11074:2005, 4.4.22.
NOTE 2 Specified time is the maximum time interval.
3.4
storage time
period of time between filling of the sample container and further treatment of the sample in the
laboratory, if stored under predefined conditions
NOTE 1 Sampling finishes as soon as the sample container has been filled with the sample. Storage time ends
when the sample is taken by the analyst to start sample preparation prior to analysis.
NOTE 2 Further treatment is, for most analytes, a solvent extraction or acid destruction. The initial steps
of sample preparation can be steps complementary to the storage conditions for the maintenance of analyte
concentrations.
4 Sampling and chain of custody
If there is a need to take samples, this is done according to a sampling programme. The first step is to
design a sampling programme. Guidance on this topic is given in ISO 5667-1.
Depending on the sample type and matrix, the guidelines found in the relevant part(s) of ISO 5667 and
ISO 19458 shall be consulted.
The process of preservation and handling of water samples consists of several steps. During this
process, the responsibility for the samples might change. To ensure the integrity of the samples, all steps
involving the sample shall be documented.
All preparation procedures shall be checked to ensure positive or negative interferences do not occur.
As a minimum, this shall include the analysis of blanks (e.g. field blank or sample container) or samples
containing known levels of relevant analytes as specified in ISO 5667-14.
5 Reagents and materials
WARNING — Certain preservatives (e.g. acids, alkalis, formaldehyde) need to be used with
caution. Sampling personnel should be warned of potential dangers, and appropriate safety
procedures should be followed.
The following reagents are used for the sample preservation and shall only be prepared according to
individual sampling requirements. All reagents used shall be of at least analytical reagent grade and
water shall be of at least ISO 3696, grade 2. Acids referred to in this part of ISO 5667 are commercially
available “concentrated” acids.
All reagents shall be labelled with a “shelf-life”. The shelf-life represents the period for which the reagent
is suitable for use, if stored correctly. This shelf-life shall not be exceeded. Any reagents that are not
completely used by the expiry of the shelf-life date shall be discarded.
NOTE Often the shelf-life of reagents is supplied by the receiving laboratory.
Check reagents periodically, e.g. by field blanks, and discard any reagent found to be unsuitable.
Between on-site visits, reagents shall be stored separately from sample containers and other equipment
in a clean, secure cabinet in order to prevent contamination.
Each sample shall be labelled accordingly, after the addition of the preservative. Otherwise, there could
be no visible indication as to which samples have been preserved, and which have not.
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ISO/FDIS 5667-3:2012(E)
5.1 Solids
5.1.1 Sodium thiosulfate pentahydrate, Na S O ·5H O, w(Na S O ·5H O) > 99 %.
2 2 3 2 2 2 3 2
5.1.2 Ascorbic acid, C H O , w(C H O ) > 99 %.
6 8 6 6 8 6
5.1.3 Sodium hydroxide, NaOH, w(NaOH) > 99 %.
5.1.4 Sodium tetraborate decahydrate, Na B O ·10H O, w(Na B O ·10H O), > 99 %.
2 4 7 2 2 4 7 2
CAUTION Sodium tetraborate decahydrate is known to be a carcinogen, mutagen and
reproductive toxin (CMR).
5.1.5 Hexamethylenetetramine (hexamine, urotropine), C H N , w(C H N ) > 99 %.
6 12 4 6 12 4
5.1.6 Potassium iodide, KI, w(KI) > 99 %.
5.1.7 Iodine, I , w(I ) > 99 %.
2 2
5.1.8 Sodium acetate, C H NaO , w(C H NaO ) > 99 %.
2 3 2 2 3 2
5.1.9 Ethylenediamine, C H N , w(C H N ) > 99 %.
2 8 2 2 8 2
5.2 Solutions
5.2.1 Zinc acetate solution C H O Zn (10 g/l).
4 6 4
Dissolve 10,0 g of zinc acetate in ∼100 ml of water . Dilute to the mark with water. Store the solution in a
polypropylene or glass bottle for a maximum period of 1 a.
5.2.2 Orthophosphoric acid (ρ ≈ 1,7 g/ml), H PO , w(H PO ) > 85 %, c(H PO ) = 15 mol/l.
3 4 3 4 3 4
5.2.3 Hydrochloric acid (ρ ≈ 1,2 g/ml), HCl, w(HCl) > 36 %, c(HCl) = 12,0 mol/l.
5.2.4 Nitric acid (ρ ≈ 1,42 g/ml), HNO , w(HNO3) > 65 %, c(HNO ) = 15,8 mol/l.
3 3
5.2.5 Sulfuric acid (ρ ≈ 1,84 g/ml), H SO (freshly prepared).
2 4
Dilute concentrated sulfuric acid (H SO ), ρ ≈ 1,84 g/ml, w(H SO ) ≈ 98 % 1 + 1 by carefully adding the
2 4 2 4
concentrated acid to an equal volume of water and mix.
WARNING — Adding the concentrated acid to the water can give violent reactions because of an
exothermic reaction.
5.2.6 Sodium hydroxide solution (ρ ≈ 0,40 g/ml), NaOH.
5.2.7 Formaldehyde solution (formalin), CH O, ϕ(CH O) = 37 % to 40 % (freshly prepared),
2 2
WARNING — Beware of formaldehyde vapours. Do not store large numbers of samples in
small work areas.
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ISO/FDIS 5667-3:2012(E)
5.2.8 Disodium salt of ethylenediaminetetraacetic acid (EDTA) (ρ ≈ 0,025 g/ml),
C H N Na O ⋅2H O, w(C H N Na O ⋅2H O) > 99 %.
10 14 2 2 8 2 10 14 2 2 8 2
Dissolve 25 g EDTA in 1 000 ml of water.
5.2.9 Ethanol C H OH, ϕ(C H OH) = 96 %.
2 5 2 5
5.2.10 Alkaline Lugol’s solution, 100 g potassium iodide (5.1.6), 50 g iodine (5.1.7), and 250 g sodium
acetate (5.1.8) in 1 000 ml water to pH 10.
5.2.11 Acidic Lugol’s solution, 100 g potassium iodide (5.1.6), 50 g iodine (5.1.7) and 100 ml glacial
acetic acid (5.2.17) in 1 000 ml water to pH 2.
5.2.12 Neutralized formaldehyde solution, formaldehyde solution (5.2.7) neutralized with sodium
tetraborate (5.1.4) or hexamethylenetetramine (5.1.5). Formalin solution at 100 g/l gives a final solution
of ϕ(CH O) = 3,7 % to 4,0 %.
2
WARNING — Beware of formaldehyde vapours. Do not store large numbers of samples in
small work areas.
5.2.13 Ethanol preservative solution.
Ethanol (5.2.9), formaldehyde solution (5.2.7) and glycerol (5.2.18) (100 + 2 + 1 parts by volume,
respectively).
5.2.14 Sodium hypochlorite NaOCl, w(NaOCl) = 10 %. Dissolve 100 g sodium hypochlorite (NaOCl) in
1 000 ml of water.
5.2.15 Potassium iodate KIO , w(KIO ) = 10 %. Dissolve 100 g potassium iodate (KIO ) in 1 000 ml of water.
3 3 3
5.2.16 Methanoic acid (formic acid) CH O , ϕ(CH O ) > 98 %.
2 2 2 2
5.2.17 Glacial acetic acid C H O , w(C H O ) > 99 %.
2 4 2 2 4 2
5.2.18 Glycerol (glycerin, glycerine) C H (OH ).
3 5 3
5.3 Materials
5.3.1 Container and cap, types as specified in Tables A.1 to A.3.
5.3.2 Filter, pore size 0,40 µm to 0,45 µm, unless a different filter size is specified in the analytical
International Standard.
6 Containers
6.1 Container selection and preparation
The choice of sample container (5.3.1) is of major importance and ISO 5667-1 provides some guidance
on this subject.
Details of the type of container used for the collection and storage of samples are given in Tables A.1 to
A.3. The same considerations given to this selection of suitable container material shall also be given to
the selection of cap liner materials.
4 © ISO 2012 – All rights reserved
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ISO/FDIS 5667-3:2012(E)
Sample containers shall be made of a material appropriate for preserving the natural properties of both
the sample and the expected range of contaminants. Suitable types of containers for each analyte to be
measured are given in Tables A.1 to A.3.
NOTE For very low concentrations of metals, containers prescribed can be different from those used for
higher concentrations. Details can be found in Table A.1 or in the analytical International Standards.
If the samples are to be frozen, suitable containers, such as polyethylene (PE) or polytetrafluoroethylene
(PTFE), shall be used to prevent breakage.
The use of disposables is preferred. Some manufacturers supply containers with a certificate of
cleanliness. If such a certificate of cleanliness is supplied, it is not necessary to clean or rinse the
containers before use.
6.2 Filtration on site
Filtration on site is required in some cases.
— Groundwaters shall be filtered on site if dissolved metals need to be analysed.
— Waters shall be filtered (5.3.2) on site, if this is required according to Annex A. Unless specified
otherwise, a filter pore size 0,40 µm to 0,45 µm shall be used.
If immediate filtration on site is impossible, then the reason and the time between sampling and filtration
shall be added to the test report.
6.3 Filling the container
The container (5.3.1) shall be filled completely unless prescribed differently in Tables A.1 to A.3 or the
analytical International Standard used. If the samples are to be frozen as part of their preservation,
sample containers shall not be completely filled. This is in order to prevent breakage which may arise
from expansion of ice during the freezing and thawing process.
If no preservatives are present in the bottle, then prerinsing the bottle may be advisable. Guidance on
prerinsing can be found in ISO 5667-14.
7 Sample handling and preservation
7.1 Sample handling and preservation for physical and chemical examination
Waters, particularly fresh waters, waste waters and groundwaters, are susceptible to changes as a result
of physical, chemical or biological reactions which may take place between the time of sampling and the
commencement of analysis. The nature and rate of these reactions are often such that, if precautions are
not taken during sampling, transport and storage (for specific analytes), the concentrations determined
are different to those existing at the time of sampling.
The extent of these changes is dependent on the chemical and biological nature of the sample, its
temperature, its exposure to light, the type of the container in which it is placed, the time between
sampling and analysis, and the conditions to which it is subjected, e.g. agitation during transport.
Further specific causes of variation are listed in a) to f).
a) The presence of bacteria, algae and other organisms can consume certain constituents of the samples.
These organisms can also modify the nature of the constituents to produce new constituents. This
biological activity affects, for example, the concentrations of dissolved oxygen, carbon dioxide,
compounds of nitrogen, phosphorus and, sometimes, silicon.
b) Certain compounds can be oxidized either by dissolved oxygen present in the samples, or by
atmospheric oxygen [e.g. organic compounds, Fe(II) and sulfides].
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ISO/FDIS 5667-3:2012(E)
c) Certain substances can precipitate out of solution, e.g. calcium carbonate, metals, and metallic
compounds such as Al(OH) , or can be lost to the vapour phase (e.g. oxygen, cyanides, and mercury).
3
d) Absorption of carbon dioxide from air can modify pH, conductivity, and the concentration of
dissolved carbon dioxide. Passage of compounds like ammonia and silicon fluoride through some
types of plastics may also affect pH or conductivity.
e) Dissolved metals or metals in a colloidal state, as well as certain organic compounds, can be
irreversibly adsorbed on to the surface of the containers or solid materials in the samples.
f) Polymerized products can depolymerize, and conversely, simple compounds can polymerize.
Changes to particular constituents vary both in degree and rate, not only as a function of the type of
water, but also, for the same water type, as a function of seasonal conditions.
These changes are often sufficiently rapid to modify the sample considerably in a short time. In all cases,
it is essential to take precautions to minimize these reactions and, in the case of many analytes, to
analyse the sample with a minimum of delay. If the required precaution for changes is filtration on site,
then a filter (5.3.2) shall be used.
Details of the sample preservation are given in Table A.1.
7.2 Sample handling and preservation for biological examination
The handling of samples for biological examination is different from that for samples requiring chemical
analysis. The addition of chemicals to the sample for biological examination can be used for either fixation
and/or preservation of the sample. The term “fixation” is defined as the protection of morphological
structures, while the term “preservation” is defined as the protection of organic matter from biochemical
or chemical degradation. Preservatives, by definition, are toxic, and the addition of preservatives may
lead to the death of living organisms. Prior to death, irritation may cause the most delicate organisms,
which do not have strong cell walls, to collapse before fixation is complete. To minimize this effect, it is
important that the fixation agent enter the cell quickly.
IMPORTANT Acidic Lugol’s solutions (5.2.11) can lead to the loss of structures in organisms or also
lead to the loss of small organisms (e.g. some flagellates); in this case, use an alkaline Lugol’s solution
(5.2.10), e.g. during the summer, when the appearance of silico-flagellates is frequently observed.
The fixing and/or preservation of samples for biological examination shall meet the following criteria:
a) the effect of the fixative, and/or preservative, on the loss of the organism shall be known beforehand;
b) the fixative or preservative shall effectively prevent the biological degradation of organic matter at
least during the storage period of the samples;
c) the fixative, and/or preservative, shall enable the biological analyte (e.g. organisms or taxonomical
groups) to be assessed during the storage period of the samples.
Details of the preservation of samples are given in Table A.2.
7.3 Sample handling and preservation for radiochemical analysis
WARNING — Radioprotection such as shielding may be necessary, depending on the activity
of the sample.
There is little difference between the handling of samples for radiochemical analysis and the handling
of samples for physicochemical analysis.
6 © ISO 2012 – All rights reserved
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ISO/FDIS 5667-3:2012(E)
The delay between sampling and measurement has to be consistent with the radioactive half-life of
the radionuclides of interest. The conditions to be taken for adequate storage are independent of the
radioactive half-life, but identical to those required for the corresponding stable isotope.
NOTE Cooling radiological samples is primarily used to prevent algal growth and biological spoilage. It is
not a necessary preservation step for radiochemical analyses. These samples are often combined with those for
physical, chemical or biological analysis.
8 Sample transport
Cooling or freezing procedures shall be applied to samples to increase the time period available for
transport and storage and if required by Tables A.1 to A.3. When transport takes place, the sampling
plan (e.g. ISO 5667-1) shall consider:
— the time between sampling and start of transport;
— transport time;
— starting time of analysis in the laboratory.
This sum of these three periods is limited to the maximum storage times according to Tables A.1 to A.3.
If the maximum storage time cannot be met, then the sampling plan shall be reformulated to allow these
requirements to be accommodated.
A cooling temperature of the device during transport of (5 ± 3) °C has been found suitable for many
applications. Cooling and freezing procedures applied shall be in line with instructions from t
...
NORME ISO
INTERNATIONALE 5667-3
Quatrième édition
2012-11-15
Qualité de l’eau — Échantillonnage —
Partie 3:
Conservation et manipulation des
échantillons d’eau
Water quality — Sampling —
Part 3: Preservation and handling of water samples
Numéro de référence
ISO 5667-3:2012(F)
©
ISO 2012
---------------------- Page: 1 ----------------------
ISO 5667-3:2012(F)
DOCUMENT PROTÉGÉ PAR COPYRIGHT
© ISO 2012
Droits de reproduction réservés. Sauf indication contraire, aucune partie de cette publication ne peut être reproduite ni utilisée
sous quelque forme que ce soit et par aucun procédé, électronique ou mécanique, y compris la photocopie, l’affichage sur
l’internet ou sur un Intranet, sans autorisation écrite préalable. Les demandes d’autorisation peuvent être adressées à l’ISO à
l’adresse ci-après ou au comité membre de l’ISO dans le pays du demandeur.
ISO copyright office
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Tel. + 41 22 749 01 11
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Version française parue en 2013
Publié en Suisse
ii © ISO 2012 – Tous droits réservés
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ISO 5667-3:2012(F)
Sommaire Page
Avant-propos .iv
Introduction .vi
1 Domaine d’application . 1
2 Références normatives . 1
3 Termes et définitions . 1
4 Échantillonnage et chaîne de surveillance . 2
5 Réactifs et matériel . 2
5.1 Solides. 3
5.2 Solutions . 3
5.3 Matériel . 4
6 Récipients . 5
6.1 Choix et préparation du récipient. 5
6.2 Filtration sur site . 5
6.3 Remplissage du récipient . 5
7 Manipulation et conservation des échantillons . 5
7.1 Manipulation et conservation pour l’examen physique et chimique . 5
7.2 Manipulation et conservation pour l’examen biologique . 6
7.3 Manipulation et conservation pour l’analyse radiochimique . 7
8 Transport des échantillons . 7
9 Identification des échantillons . 8
10 Réception des échantillons . 8
11 Stockage des échantillons . 9
Annexe A (informative) Techniques de conservation des échantillons .10
Annexe B (informative) Préparation des récipients .46
Annexe C (informative) Protocole utilisé dans les études de validation hollandaises .48
Bibliographie .50
© ISO 2012 – Tous droits réservés iii
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ISO 5667-3:2012(F)
Avant-propos
L’ISO (Organisation internationale de normalisation) est une fédération mondiale d’organismes
nationaux de normalisation (comités membres de l’ISO). L’élaboration des Normes internationales est
en général confiée aux comités techniques de l’ISO. Chaque comité membre intéressé par une étude
a le droit de faire partie du comité technique créé à cet effet. Les organisations internationales,
gouvernementales et non gouvernementales, en liaison avec l’ISO participent également aux travaux.
L’ISO collabore étroitement avec la Commission électrotechnique internationale (CEI) en ce qui concerne
la normalisation électrotechnique.
Les Normes internationales sont rédigées conformément aux règles données dans les Directives
ISO/CEI, Partie 2.
La tâche principale des comités techniques est d’élaborer les Normes internationales. Les projets de
Normes internationales adoptés par les comités techniques sont soumis aux comités membres pour vote.
Leur publication comme Normes internationales requiert l’approbation de 75 % au moins des comités
membres votants.
L’attention est appelée sur le fait que certains des éléments du présent document peuvent faire l’objet de
droits de propriété intellectuelle ou de droits analogues. L’ISO ne saurait être tenue pour responsable de
ne pas avoir identifié de tels droits de propriété et averti de leur existence.
L’ISO 5667-3 a été élaborée par le comité technique ISO/TC 147, Qualité de l’eau, sous-comité SC 6,
Échantillonnage (méthodes générales).
Cette quatrième édition annule et remplace la troisième édition (ISO 5667-3:2003), qui a fait l’objet d’une
révision technique.
L’ISO 5667 comprend les parties suivantes, présentées sous le titre général Qualité de l’eau —
Échantillonnage:
— Partie 1: Lignes directrices pour la conception des programmes et des techniques d’échantillonnage
— Partie 3: Lignes directrices pour la conservation et la manipulation des échantillons d’eau
— Partie 4: Guide pour l’échantillonnage des eaux des lacs naturels et des lacs artificiels
— Partie 5: Lignes directrices pour l’échantillonnage de l’eau potable des usines de traitement et du réseau
de distribution
— Partie 6: Lignes directrices pour l’échantillonnage des rivières et des cours d’eau
— Partie 7: Guide général pour l’échantillonnage des eaux et des vapeurs dans les chaudières
— Partie 8: Guide général pour l’échantillonnage des dépôts humides
— Partie 9: Guide pour l’échantillonnage des eaux marines
— Partie 10: Guide pour l’échantillonnage des eaux résiduaires
— Partie 11: Lignes directrices pour l’échantillonnage des eaux souterraines
— Partie 12: Guide général pour l’échantillonnage des sédiments
— Partie 13: Lignes directrices pour l’échantillonnage de boues
— Partie 14: Lignes directrices pour le contrôle de la qualité dans l’échantillonnage et la manutention des
eaux environnementales
— Partie 15: Lignes directrices pour la conservation et le traitement des échantillons de boues et de sédiments
— Partie 16: Lignes directrices pour les essais biologiques des échantillons
iv © ISO 2012 – Tous droits réservés
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ISO 5667-3:2012(F)
— Partie 17: Lignes directrices pour l’échantillonnage des matières solides en suspension
— Partie 19: Lignes directrices pour l’échantillonnage des sédiments en milieu marin
— Partie 20: Lignes directrices relatives à l’utilisation des données d’échantillonnage pour la prise de
décision — Conformité avec les limites et systèmes de classification
— Partie 21: Lignes directrices pour l’échantillonnage de l’eau potable distribuée par camions-citernes ou
d’autres moyens que les tuyaux de distribution
— Partie 22: Lignes directrices pour la conception et l’installation de points d’échantillonnage des
eaux souterraines
— Partie 23: Lignes directrices pour l’échantillonnage passif dans les eaux de surface
© ISO 2012 – Tous droits réservés v
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ISO 5667-3:2012(F)
Introduction
La présente partie de l’ISO 5667 est destinée à être utilisée conjointement avec l’ISO 5667-1 qui traite de
la conception des programmes d’échantillonnage et des techniques d’échantillonnage.
La présente partie de l’ISO 5667 a été alignée avec les normes actuelles lorsque cela était possible.
Lorsque de nouveaux résultats de recherche ou de validation ont ouvert de nouvelles perspectives, les
connaissances les plus récentes ont été utilisées.
[63]
Des lignes directrices sur les protocoles de validation sont données dans le Guide ISO 34 .
vi © ISO 2012 – Tous droits réservés
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NORME INTERNATIONALE ISO 5667-3:2012(F)
Qualité de l’eau — Échantillonnage —
Partie 3:
Conservation et manipulation des échantillons d’eau
AVERTISSEMENT — La présente partie de l’ISO 5667 et les Normes internationales d’analyse
listées dans l’Annexe A sont complémentaires. Lorsqu’aucune Norme internationale d’analyse
n’est applicable, la (les) technique(s) décrite(s) dans les Tableaux A.1 à A.3 a(ont) un statut
normatif. Lorsque des normes d’analyse nouvelles ou révisées sont développées avec des durées
de stockage ou des techniques de conservation s’écartant des Tableaux A.1 à A.3, il convient
que ces durées de stockage ou ces techniques de conservation soient validées et présentées à
l’ISO/TC 147/SC 6/WG 3 afin d’être incorporées lors de la prochaine révision de la présente partie
de l’ISO 5667.
1 Domaine d’application
La présente partie de l’ISO 5667 établit les exigences générales relatives à l’échantillonnage, la
conservation, la manipulation, le transport et le stockage de tous les échantillons d’eau, y compris ceux
destinés à des analyses biologiques. Elle ne s’applique pas aux échantillons d’eau destinés à des analyses
microbiologiques telles que spécifiées dans l’ISO 19458, des essais écotoxicologiques, des essais
biologiques et ni à l’échantillonnage passif tel que spécifié dans le domaine d’application de l’ISO 5667-23.
La présente partie de l’ISO 5667 s’applique en particulier chaque fois qu’un échantillon ponctuel ou
composite ne peut être analysé sur site et doit être transporté vers un laboratoire pour analyse.
2 Références normatives
Les documents de référence suivants sont indispensables pour l’application du présent document. Pour
les références datées, seule l’édition citée s’applique. Pour les références non datées, la dernière édition
du document de référence s’applique (y compris les éventuels amendements).
ISO 3696, Eau pour laboratoire à usage analytique — Spécification et méthodes d’essai
ISO 5667 (toutes les parties), Qualité de l’eau — Échantillonnage
ISO 19458, Qualité de l’eau — Échantillonnage pour analyse microbiologique
3 Termes et définitions
Pour les besoins du présent document, les termes et définitions suivants s’appliquent.
3.1
intégrité
propriété assurant que le(s) paramètre(s) d’intérêt, l’information ou le contenu du récipient de l’échantillon,
n’a pas été altéré ou perdu d’une manière non autorisée ou qu’aucune perte de représentativité de
l’échantillon ne s’est produite
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ISO 5667-3:2012(F)
3.2
conservation d’un échantillon
toute procédure visant à stabiliser un échantillon, c’est-à-dire à stabiliser les propriétés à étudier, depuis
l’étape du prélèvement jusqu’à celle de la préparation pour analyse
[SOURCE: ISO 11074:2005, 4.4.20]
Note 1 à l’article: Différents analytes peuvent nécessiter plusieurs échantillons provenant de la même source qui
sont stabilisés par différentes procédures.
3.3
stockage d’un échantillon
processus, et son résultat, consistant à garder un échantillon disponible dans des conditions prédéfinies,
pour un laps de temps (en général) déterminé entre le prélèvement et le traitement de cet échantillon
Note 1 à l’article: Adaptée de l’ISO 11074:2005, 4.4.22.
Note 2 à l’article: Le temps déterminé est le laps de temps maximal.
3.4
durée de stockage
période entre le remplissage du récipient et le traitement ultérieur de l’échantillon au laboratoire, si
l’échantillon est conservé dans des conditions prédéfinies
Note 1 à l’article: L’échantillonnage prend fin dès que le récipient a été rempli avec l’échantillon. La durée de
conservation prend fin lorsque l’échantillon est prélevé par l’analyste pour commencer la préparation de
l’échantillon avant l’analyse.
Note 2 à l’article: Pour la plupart des analytes, le traitement ultérieur est une extraction au solvant ou une
minéralisation à l’acide. Les étapes initiales de préparation de l’échantillon peuvent être des étapes complémentaires
aux conditions de stockage visant à stabiliser les concentrations en analytes.
4 Échantillonnage et chaîne de surveillance
Lorsqu’il est nécessaire de prélever des échantillons, cette opération doit être réalisée conformément à un
programme d’échantillonnage. La première étape consiste à concevoir un programme d’échantillonnage.
Des lignes directrices sur ce sujet sont données dans l’ISO 5667-1.
Selon le type et la matrice de l’échantillon, les lignes directrices fournies dans la (les) partie(s)
concernée(s) de l’ISO 5667 et de l’ISO 19458 doivent être consultées.
Le processus de conservation et de manipulation des échantillons d’eau comporte plusieurs étapes.
Durant ce processus la responsabilité des échantillons peut changer. Pour assurer l’intégrité des
échantillons, toutes les étapes impliquant l’échantillon doivent être documentées.
Tous les modes opératoires de préparation doivent être vérifiés pour s’assurer qu’aucune interférence
positive ou négative ne se produit. Cette opération doit au minimum inclure l’analyse de blancs (par
exemple les blancs de terrain ou blanc de récipient de l’échantillon) ou d’échantillons contenant des
niveaux connus des analytes concernés, comme spécifié dans l’ISO 5667-14.
5 Réactifs et matériel
AVERTISSEMENT — Certains conservateurs (par exemple les acides, les bases, le formaldéhyde)
doivent être utilisés avec précaution. Il convient que le personnel réalisant l’échantillonnage soit
averti des dangers potentiels et que des procédures de sécurité appropriées soient suivies.
Les réactifs suivants sont utilisés pour la conservation des échantillons. Ils doivent être préparés
conformément aux exigences relatives aux échantillonnages individuels. Tous les réactifs utilisés
doivent être au minimum de qualité analytique et l’eau doit être au minimum de qualité 2 conformément
2 © ISO 2012 – Tous droits réservés
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ISO 5667-3:2012(F)
à l’ISO 3696. Les acides auxquels il est fait référence dans la présente partie de l’ISO 5667 sont des acides
«concentrés» du commerce.
Tous les réactifs doivent porter une étiquette indiquant leur «date de péremption». La «date de
péremption» correspond à une période pendant laquelle le réactif est utilisable, dans la mesure où il
est stocké correctement. Cette date de péremption ne doit pas être dépassée. Tout réactif qui n’a pas été
complètement utilisé à l’expiration du délai de péremption doit être jeté.
NOTE La date de péremption des réactifs est habituellement fournie par le laboratoire de réception.
Vérifier périodiquement les réactifs, par exemple par des blancs de terrain et écarter tout réactif
jugé impropre.
Entre les visites sur site, les réactifs doivent être stockés séparément des récipients pour échantillons
et des autres équipements, dans des armoires propres et sûres, afin d’empêcher toute contamination.
Après avoir ajouté le conservateur, chaque échantillon doit être étiqueté en conséquence. Sinon, il peut
n’y avoir aucun signe visible indiquant qu’un échantillon a été stabilisé ou non.
5.1 Solides
5.1.1 Thiosulfate de sodium pentahydraté, Na S O , 5H O, w(Na S O , 5H O) > 99 %.
2 2 3 2 2 2 3 2
5.1.2 Acide ascorbique, C H O , w(C H O ) > 99 %.
6 8 6 6 8 6
5.1.3 Hydroxyde de sodium, NaOH, w(NaOH) > 99 %.
5.1.4 Tétraborate de sodium décahydraté, Na B O , 10H O, w(Na B O , 10H O), > 99 %
2 4 7 2 2 4 7 2
ATTENTION — Le tétraborate de sodium décahydraté est connu pour être une toxine cancérigène,
mutagène et reprotoxique (CMR).
5.1.5 Hexaméthylènetétramine (hexamine, urotropine), C H N , w(C H N ) > 99 %.
6 12 4 6 12 4
5.1.6 Iodure de potassium, KI, w(KI) > 99 %.
5.1.7 Iode, I w(I ) > 99 %.
2, 2
5.1.8 Acétate de sodium, C H NaO w(C H NaO ) > 99 %.
2 3 2, 2 3 2
5.1.9 Éthylènediamine, C H N , w(C H N ) > 99 %.
2 8 2 2 8 2
5.2 Solutions
5.2.1 Solution d’acétate de zinc C H O Zn (10 g/l).
4 6 4
Dissoudre 10,0 g d’acétate de zinc dans approximativement 100 ml d’eau. Compléter avec de l’eau jusqu’à
100 ml. Conserver la solution pendant un an au maximum, dans un flacon de polypropylène ou de verre.
5.2.2 Acide orthophosphorique (ρ ≈ 1,7 g/ml), H PO , w(H PO ) > 85 %, c(H PO ) = 15 mol/l.
3 4 3 4 3 4
5.2.3 Acide chlorhydrique (ρ ≈ 1,2 g/ml), HCl, w(HCl) > 36 %, c(HCl) = 12,0 mol/l.
5.2.4 Acide nitrique (ρ ≈ 1,42 g/ml), HNO w(HNO ) > 65 %, c(HNO ) = 15,8 mol/l.
3, 3 3
© ISO 2012 – Tous droits réservés 3
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ISO 5667-3:2012(F)
5.2.5 Acide sulfurique (ρ ≈1,84 g/ml), H SO (fraîchement préparé).
2 4
Diluer de l’acide sulfurique concentré (H SO ), ρ ≈1,84 g/ml, w(H SO ) ≈ 98 % 1 + 1 en ajoutant
2 4 2 4
soigneusement l’acide concentré à un volume égal d’eau et de mélange.
AVERTISSEMENT — Ajouter l’acide concentré à l’eau peut provoquer des réactions violentes du
fait d’une réaction exothermique.
5.2.6 Solution d’hydroxyde de sodium (ρ ≈ 0,40 g/ml), NaOH.
5.2.7 Solution de formaldéhyde (formol), CH O, φ(CH O) = 37 % à 40 % (fraîchement préparée).
2 2
AVERTISSEMENT — Prendre garde aux vapeurs de formaldéhyde. Ne pas stocker un grand
nombre d’échantillons dans une petite zone de travail.
5.2.8 Solution aqueuse de sel disodique d’acide éthylène diamine tétraacétique (EDTA)
(ρ ≈ 0,025 g/ml), C H N Na O , 2H O, w(C H N Na O , 2H O) > 99 %.
10 14 2 2 8 2 10 14 2 2 8 2
Dissoudre 25 g d’EDTA dans 1 000 ml d’eau.
5.2.9 Éthanol C H OH, φ(C H OH) = 96 %.
2 5 2 5
5.2.10 Solution alcaline de Lugol, 100 g d’iodure de potassium (5.1.6), 50 g d’iode (5.1.7) et 250 g
d’acétate de sodium (5.1.8) dans 1 000 ml d’eau, de pH 10.
5.2.11 Solution acide de Lugol, 100 g d’iodure de potassium (5.1.6), 50 g d’iode (5.1.7) et 100 ml d’acide
acétique glacial (5.2.17) dans 1 000 ml d’eau, de pH 2.
5.2.12 Solution de formaldéhyde neutralisé, solution de formaldéhyde (5.2.7) neutralisé au tétraborate
de sodium (5.1.4) ou à l’hexaméthylènetétramine (5.1.5). Une solution de formol à 100 g/l donne une
solution finale de φ(CH O) = 3,7 % à 4,0 %.
2
AVERTISSEMENT — Prendre garde aux vapeurs de formaldéhyde. Ne pas stocker un grand
nombre d’échantillons dans une petite zone de travail.
5.2.13 Solution de conservation à l’éthanol.
Éthanol (5.2.9), solution de formaldéhyde (5.2.7) et glycérol (5.2.18) dans les proportions de 100 + 2 + 1
(en volume) respectivement.
5.2.14 Hypochlorite de sodium NaOCl, w(NaOCl) = 10 %. Dissoudre 100 g d’hypochlorite de sodium
(NaOCl) dans 1 000 ml d’eau.
5.2.15 Iodate de potassium KIO , w(KIO ) = 10 %. Dissoudre 100 g d’iodate de potassium (KIO ) dans
3 3 3
1 000 ml d’eau.
5.2.16 Acide méthanoïque (acide formique) CH O , φ(CH O ) > 98 %.
2 2 2 2
5.2.17 Acide acétique glacial, C H O , w(C H O ) > 99 %.
2 4 2 2 4 2
5.2.18 Glycérol (glycérine) C H (OH) .
3 5 3
5.3 Matériel
5.3.1 Récipient et bouchon, de type et volumes spécifiés dans les Tableaux A.1 à A.3.
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ISO 5667-3:2012(F)
5.3.2 Filtre, de taille de pores allant de 0,40 µm à 0,45 µm, à moins qu’une taille de filtre différente ne
soit spécifiée dans la Norme internationale analytique.
6 Récipients
6.1 Choix et préparation du récipient
Le choix du récipient (5.3.1) est d’une importance capitale et l’ISO 5667-1 donne des lignes directrices
sur ce sujet.
Les Tableaux A.1 à A.3 détaillent le type de récipient utilisé pour le prélèvement et la conservation des
échantillons. Les mêmes considérations relatives au choix d’un matériau approprié pour le récipient
doivent être appliquées au choix des matériaux des couvercles.
Les récipients pour échantillon doivent être constitués d’un matériau approprié pour la préservation des
propriétés naturelles de l’échantillon et de la gamme de contaminants attendue. Les types de récipients
adaptés à chaque analyte à mesurer sont indiqués dans les Tableaux A.1 à A.3.
NOTE Pour les très faibles concentrations en métaux, les récipients spécifiés peuvent être différents de
ceux utilisés pour les concentrations plus élevées. Les détails se trouvent dans le Tableau A.1 ou les Norme
internationale d’analyses.
Si les échantillons doivent être congelés, des récipients adaptés, par exemple en polyéthylène (PE) ou en
polytétrafluoroéthylène (PTFE), doivent être utilisés pour éviter toute casse.
L’emploi de matériel à usage unique est préférable. Certains fabricants fournissent des récipients
accompagnés d’une garantie de propreté. Si un tel certificat de propreté est fourni, il n’est pas nécessaire
de nettoyer ou de rincer les récipients avant l’usage.
6.2 Filtration sur site
La filtration sur site est nécessaire dans certains cas.
— Les eaux souterraines doivent être filtrées sur site si les métaux dissous doivent être analysés.
— Les eaux doivent être filtrées (5.3.2) sur site, si cela est exigé conformément à l’Annexe A. Sauf
mention contraire, un filtre de porosité de 0,40 µm à 0,45 µm doit être utilisé.
Si la filtration immédiate sur site est impossible, alors la raison et le temps entre l’échantillonnage et la
filtration doivent être consignés dans le rapport d’essai.
6.3 Remplissage du récipient
Le récipient (5.3.1) doit être entièrement rempli, sauf spécification contraire dans les Tableaux A.1 à A.3
ou dans la Norme internationale d’analyse utilisée. S’il est nécessaire de congeler les échantillons afin de
les préserver, les récipients des échantillons ne doivent pas être entièrement remplis, afin d’éviter qu’ils
ne se brisent durant la procédure de gel-dégel.
Si aucun agent de conservation n’est présent dans le flacon, il est conseillé de rincer le flacon au préalable.
Les lignes directrices relatives au pré-rinçage sont données dans l’ISO 5667-14.
7 Manipulation et conservation des échantillons
7.1 Manipulation et conservation pour l’examen physique et chimique
Toutes les eaux, en particulier les eaux superficielles, les eaux résiduaires et les eaux souterraines, sont
susceptibles de se modifier par suite de réactions physiques, chimiques ou biologiques qui peuvent avoir
lieu entre l’instant du prélèvement et le début de l’analyse. La nature et l’intensité de ces réactions sont
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ISO 5667-3:2012(F)
souvent telles que, si les précautions nécessaires ne sont pas prises pendant l’échantillonnage, le transport
et le stockage (pour des analytes spécifiques), les concentrations déterminées seront différentes de ce
qu’elles étaient au moment du prélèvement.
L’importance de ces modifications dépend de la nature chimique et biologique de l’échantillon, de sa
température, de son exposition à la lumière, de la nature du récipient, du temps qui sépare le prélèvement
de l’analyse, et des conditions auxquelles il est soumis, par exemple l’agitation au cours du transport.
D’autres causes spécifiques de variations existent et sont énumérées de a) à f).
a) La présence de bactéries, d’algues et d’autres organismes peuvent consommer certains constituants
des échantillons. Ces organismes peuvent aussi modifier la nature des constituants et donner ainsi
naissance à de nouveaux constituants. Cette activité biologique affecte, par exemple, les teneurs en
oxygène dissous, en dioxyde de carbone dissous, en composés azotés, phosphorés et parfois en silicium.
b) Certains composés peuvent être oxydés par l’oxygène dissous présent dans les échantillons ou par
l’oxygène de l’air [par exemple les composés organiques, le fer(II) et les sulfures].
c) Certaines substances peuvent quitter la phase dissoute par précipitation [par exemple le carbonate
de calcium, les métaux ou les composés métalliques tels que Al(OH) ] ou s’échapper des échantillons
3
par évaporation (par exemple l’oxygène, les cyanures et le mercure).
d) L’absorption du dioxyde de carbone de l’air peut modifier le pH, la conductivité et la teneur en
dioxyde de carbone dissous. Le transfert de composés tels que l’ammoniac et le fluorure de silicium
à travers certains types de matières plastiques peut également avoir une incidence sur le pH ou la
conductivité.
e) Les métaux dissous ou à l’état colloïdal, ainsi que certains composés organiques, peuvent être
adsorbés de façon irréversible à la surface des récipients ou des matières solides contenues dans les
échantillons.
f) Les produits polymérisés peuvent se dépolymériser et, inversement, les composés simples peuvent
se polymériser.
Il s’ensuit que les variations relatives à un constituant donné sont plus ou moins importantes et rapides,
non seulement en fonction des types d’eaux, mais aussi, pour un même type d’eau, en fonction des
conditions saisonnières.
Ces changements sont souvent suffisamment rapides pour altérer considérablement l’échantillon sur
une courte période. Il est donc indispensable de prendre, dans tous les cas, les précautions nécessaires
pour que ces réactions soient les plus faibles possible et, dans le cas de la détermination de nombreux
analytes, d’analyser l’échantillon le plus rapidement possible. Si la précaution requise pour limiter les
variations est une filtration sur site, un filtre (5.3.2) doit alors être utilisé.
Les informations détaillées relatives à la conservation des échantillons sont données dans le Tableau A.1.
7.2 Manipulation et conservation pour l’examen biologique
La manipulation des échantillons destinés à un examen biologique est différente de celle des échantillons
nécessitant une analyse chimique. Des produits chimiques peuvent être ajoutés aux échantillons destinés
à un examen biologique pour la fixation et/ou la conservation de ces derniers. Le terme «fixation»
fait référence à la protection des structures morphologiques, alors que le terme «conservation» fait
référence à la protection de la matière organique contre les dégradations biochimiques ou chimiques.
Par définition, les conservateurs (ou agents de conservation) sont toxiques, et leur ajout peut entraîner
la mort des organismes vivants. Du fait de cette agression, les organismes les plus fragiles, dépourvus
de parois cellulaires robustes, peuvent se rompre avant que la fixation ne soit achevée. Afin de réduire
cet effet, il est important que l’agent de fixation pénètre rapidement dans la cellule.
IMPORTANT — Une solution acide de Lugol (5.2.11), par exemple, peut mener à une perte de
structures des organismes ou également à une perte de petits organismes (par exemple certains
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ISO 5667-3:2012(F)
flagellés); dans ce cas, utiliser des solutions alcalines de Lugol (5.2.10), par exemple pendant la
période estivale où des silico-flagellés sont fréquemment observés.
La fixation et/ou la conservation des échantillons destinés à un examen biologique doivent remplir les
critères suivants:
a) l’effet du fixateur et/ou du conservateur sur la perte des organismes doit être connu à l’avance;
b) le fixateur ou le conserva
...
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