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   <dataset id="HF043">
      <alternateIdentifier system="https://doi.org">doi:10.6073/pasta/5867ab3f5de90cb2a7366660e06f8399</alternateIdentifier>
      <title>Carbon Biogeochemistry of Forested Headwater Streams at Harvard Forest 2006-2007</title>
      <creator>
         <individualName>
            <givenName>Peter</givenName>
            <surName>Raymond</surName>
         </individualName>
         <userId directory="https://orcid.org">https://orcid.org/0000-0002-8564-7860</userId>
      </creator>
      <creator>
         <individualName>
            <givenName>William</givenName>
            <surName>Sobczak</surName>
         </individualName>
      </creator>
      <associatedParty>
         <individualName>
            <givenName>Emery</givenName>
            <surName>Boose</surName>
         </individualName>
         <userId directory="https://orcid.org">https://orcid.org/0000-0003-4820-0231</userId>
         <role>Researcher</role>
      </associatedParty>
      <pubDate>2023</pubDate>
      <language>English</language>
      <abstract>
         <section>
            <para>Headwater streams make up greater than 80% of total channel length in the United States and play important roles in regulating nutrient, organic matter, and sediment fluxes from terrestrial to downstream ecosystems. Headwater streams are common features of many upland-forested watersheds in New England, yet are not explicitly factored into forest water, carbon, and nutrient budgets. Here we report on recent efforts to examine terrestrial and stream ecosystem linkages in carbon biogeochemistry in a hemlock-dominated watershed. A prototype stream biogeochemical system (SBS) was tested at the Harvard Forest LTER. The SBS allows a suite of stream water properties to be characterized in real-time over extended periods of time thus allowing questions to be asked at a wide range of time scales. The prototype SBS was field-tested in Bigelow Brook West on the Prospect Hill research tract at Harvard Forest. Bigelow Brook West was selected because the watershed’s hydrology, stream ecology, forest composition, land-use history, and carbon sequestration have been characterized, thus aiding the interpretation of SBS data and facilitating multi-disciplinary research. The prototype system monitors stream and air temperature, pCO2 , colored dissolved organic matter, total suspended sediments, PAR, water depth, pH, and dissolved O2. Independent estimates of organic and inorganic water chemistry were used to validate and interpret SBS data. </para>
            <para>Here we report on preliminary findings from the pilot SBS at Harvard Forest to highlight the usefulness of headwater stream chemistry data to a wide-diversity of ecosystem scientists. 1) Low pH constrains dissolved inorganic carbon solute fluxes to downstream ecosystems. 2) CO2 concentrations were always supersaturated in Bigelow Brook, averaging about 6x atmospheric values in summer, thus the stream is an important source of CO2 to the atmosphere. Variation in CO2 appears to be linked to multiple mechanisms including changes in stream temperature, soil CO2, and in-stream processes. 3) Diurnal variation in stream dissolved oxygen concentrations is linked to both in situ stream processes and watershed processes, such as evapotranspiration. 4) Colored dissolved organic matter (CDOM) concentrations were tightly linked to discharge with concentrations increasing with discharge. The surprising additive effect of increasing DOC concentration with discharge cause DOC fluxes to increase non-linearly with water fluxes in Bigelow Brook. 5) Low inorganic N and P concentrations suggest that organic N and P may account for a disproportionate fraction of N and P fluxes to downstream ecosystems. Preliminary SBS data have already altered our conceptual model regarding terrestrial and aquatic linkages in the Bigelow Brook watershed and have illuminated a fundamental lack of understanding of the mechanisms regulating diurnal and storm-driven stream water chemistry in hemlock-dominated watersheds.</para>
         </section>
      </abstract>
      <keywordSet>
         <keyword>biogeochemistry</keyword>
         <keyword>carbon</keyword>
         <keyword>carbon dioxide</keyword>
         <keyword>nitrogen</keyword>
         <keyword>oxygen</keyword>
         <keyword>ph</keyword>
         <keyword>phosphorus</keyword>
         <keyword>storms</keyword>
         <keyword>stream discharge</keyword>
         <keywordThesaurus>LTER controlled vocabulary</keywordThesaurus>
      </keywordSet>
      <keywordSet>
         <keyword>organic matter</keyword>
         <keyword>inorganic nutrients</keyword>
         <keywordThesaurus>LTER core area</keywordThesaurus>
      </keywordSet>
      <keywordSet>
         <keyword>Harvard Forest</keyword>
         <keyword>HFR</keyword>
         <keyword>LTER</keyword>
         <keyword>USA</keyword>
         <keywordThesaurus>HFR default</keywordThesaurus>
      </keywordSet>
      <intellectualRights>
         <section>
            <para>This dataset is released to the public under Creative Commons CC0 1.0 (No Rights Reserved). Please keep the dataset creators informed of any plans to use the dataset. Consultation with the original investigators is strongly encouraged. Publications and data products that make use of the dataset should include proper acknowledgement.</para>
         </section>
      </intellectualRights>
      <licensed>
         <licenseName>Creative Commons Zero v1.0 Universal</licenseName>
         <url>https://spdx.org/licenses/CC0-1.0.html</url>
         <identifier>CC0-1.0</identifier>
      </licensed>
      <distribution>
         <online>
            <url function="information">https://harvardforest.fas.harvard.edu/exist/apps/datasets/showData.html?id=hf043</url>
         </online>
      </distribution>
      <coverage>
         <geographicCoverage>
            <geographicDescription>Prospect Hill Tract (Harvard Forest). Coordinates based on WGS84 datum.</geographicDescription>
            <boundingCoordinates>
               <westBoundingCoordinate>-72.20</westBoundingCoordinate>
               <eastBoundingCoordinate>-72.17</eastBoundingCoordinate>
               <northBoundingCoordinate>+42.55</northBoundingCoordinate>
               <southBoundingCoordinate>+42.53 </southBoundingCoordinate>
               <boundingAltitudes>
                  <altitudeMinimum>280</altitudeMinimum>
                  <altitudeMaximum>420</altitudeMaximum>
                  <altitudeUnits>meter</altitudeUnits>
               </boundingAltitudes>
            </boundingCoordinates>
         </geographicCoverage>
         <temporalCoverage>
            <rangeOfDates>
               <beginDate>
                  <calendarDate>2006</calendarDate>
               </beginDate>
               <endDate>
                  <calendarDate>2007</calendarDate>
               </endDate>
            </rangeOfDates>
         </temporalCoverage>
      </coverage>
      <maintenance>
         <description>
            <para>complete</para>
         </description>
      </maintenance>
      <contact scope="document">
         <positionName>Information Manager</positionName>
         <organizationName>Harvard Forest</organizationName>
         <address scope="document">
            <deliveryPoint>324 North Main Street</deliveryPoint>
            <city>Petersham</city>
            <administrativeArea>MA</administrativeArea>
            <postalCode>01366</postalCode>
            <country>USA</country>
         </address>
         <phone phonetype="voice">(978) 724-3302</phone>
         <electronicMailAddress>hf-im@lists.fas.harvard.edu</electronicMailAddress>
      </contact>
      <publisher scope="document">
         <organizationName>Harvard Forest</organizationName>
         <address scope="document">
            <deliveryPoint>324 North Main Street</deliveryPoint>
            <city>Petersham</city>
            <administrativeArea>MA</administrativeArea>
            <postalCode>01366</postalCode>
            <country>USA</country>
         </address>
         <phone phonetype="voice">(978) 724-3302</phone>
         <phone phonetype="fax">(978) 724-3595</phone>
         <onlineUrl>https://harvardforest.fas.harvard.edu</onlineUrl>
      </publisher>
      <methods>
         <methodStep>
            <description>
               <section>
                  <title>Stream Biogeochemical System (SBS)</title>
                  <para>The proto-type system monitors stream and air temperature, pCO2 (IR detector with an air headspace equilibrator, gas standard tanks are included for standardized measurements), pH in triplicate (therefore allows for the calculation of carbonate alkalinity and dissolved inorganic carbon with monthly on site calibration), colored dissolved organic matter (CDOM; fluorescence measurement which can be used as a proxy for DOC), total suspended sediments (TSS), chlorophyll a (by fluorescence), PAR, water flux (estimated from water depth) and dissolved O2 (using an optode).  The control unit (Campbell Scientific CR3000, with programmable valves) can be programmed to measure these variables at any time interval.  The current system can run for ~1 month using two marine batteries and making measurements every 2 hours.  In addition, we have independently characterized stream chemistry with monthly grab samples in which the following constituents are analyzed: dissolved organic C (Shimadzu high-temperature combustion), N, and P, and inorganic N and P (EPA methods 350.1, 353.2, and 365.1 using an Astoria2 segmented flow analyzer).</para>
               </section>
               <section>
                  <title>Stream Discharge</title>
                  <para>The Harvard Forest has initiated long-term hydrological studies on two small headwater streams in the Prospect Hill Tract.  The upper watershed on Bigelow Brook (the focus of this biogeochemical data set) comprises 24 ha of upland forest with no large wetlands.  For details see dataset HF070.</para>
               </section>
            </description>
         </methodStep>
      </methods>
      <project>
         <title>Harvard Forest Long-Term Ecological Research</title>
         <personnel>
            <organizationName>Harvard Forest</organizationName>
            <address>
               <deliveryPoint>324 North Main Street</deliveryPoint>
               <city>Petersham</city>
               <administrativeArea>MA</administrativeArea>
               <postalCode>01366</postalCode>
               <country>USA</country>
            </address>
            <phone phonetype="voice">(978) 724-3302</phone>
            <phone phonetype="fax">(978) 724-3595</phone>
            <onlineUrl>https://harvardforest.fas.harvard.edu</onlineUrl>
            <userId directory="https://ror.org">https://ror.org/059cpzx98</userId>
            <role>pointOfContact</role>
         </personnel>
         <abstract>The Harvard Forest Long-Term Ecological Research (LTER) program examines ecological dynamics in the New England region resulting from natural disturbances, environmental change, and human impacts.</abstract>
         <funding>National Science Foundation LTER grants: DEB-8811764, DEB-9411975, DEB-0080592, DEB-0620443, DEB-1237491, DEB-1832210.</funding>
      </project>
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         <entityDescription>water chemistry</entityDescription>
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               <online>
                  <url function="download">https://harvardforest.fas.harvard.edu/data/p04/hf043/hf043-01-chemistry.csv</url>
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            </distribution>
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         <attributeList>
            <attribute id="1240580800407">
               <attributeName>stream</attributeName>
               <attributeDefinition>stream location</attributeDefinition>
               <measurementScale>
                  <nominal>
                     <nonNumericDomain>
                        <enumeratedDomain>
                           <codeDefinition>
                              <code>Head of Flow</code>
                              <definition>groundwater input to Bigelow Brook West</definition>
                           </codeDefinition>
                           <codeDefinition>
                              <code>Upper Weir</code>
                              <definition>headwaters of Bigelow Brook West</definition>
                           </codeDefinition>
                           <codeDefinition>
                              <code>Lower Weir</code>
                              <definition>downstream of beaver wetland along Bigelow Brook</definition>
                           </codeDefinition>
                           <codeDefinition>
                              <code>Bigelow Brook (East)</code>
                              <definition>Bigelow Brook East @ road</definition>
                           </codeDefinition>
                           <codeDefinition>
                              <code>Nelson Brook</code>
                              <definition>Nelson Brook weir</definition>
                           </codeDefinition>
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               <attributeName>date</attributeName>
               <attributeDefinition>date</attributeDefinition>
               <measurementScale>
                  <dateTime>
                     <formatString>YYYY-MM-DD</formatString>
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            <attribute id="1240580800439">
               <attributeName>am.pm</attributeName>
               <attributeDefinition>am or pm</attributeDefinition>
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                  <nominal>
                     <nonNumericDomain>
                        <enumeratedDomain>
                           <codeDefinition>
                              <code>AM</code>
                              <definition>~ 10:00am</definition>
                           </codeDefinition>
                           <codeDefinition>
                              <code>PM</code>
                              <definition>~ 4:00pm</definition>
                           </codeDefinition>
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                     </nonNumericDomain>
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            </attribute>
            <attribute id="1240580800454">
               <attributeName>time</attributeName>
               <attributeDefinition>time sampled during storm events</attributeDefinition>
               <measurementScale>
                  <dateTime>
                     <formatString>hh:mm</formatString>
                  </dateTime>
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               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
            <attribute id="1240580800470">
               <attributeName>doc</attributeName>
               <attributeDefinition>dissolved organic carbon</attributeDefinition>
               <measurementScale>
                  <ratio>
                     <unit>
                        <standardUnit>milligramsPerLiter</standardUnit>
                     </unit>
                     <precision>0.01</precision>
                     <numericDomain>
                        <numberType>real</numberType>
                     </numericDomain>
                  </ratio>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
            <attribute id="1240580800485">
               <attributeName>total.n</attributeName>
               <attributeDefinition>NO3 + NH4 + Dissolved organic N</attributeDefinition>
               <measurementScale>
                  <ratio>
                     <unit>
                        <standardUnit>milligramsPerLiter</standardUnit>
                     </unit>
                     <precision>0.001</precision>
                     <numericDomain>
                        <numberType>real</numberType>
                     </numericDomain>
                  </ratio>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
            <attribute id="1240580800501">
               <attributeName>no3</attributeName>
               <attributeDefinition>nitrate. Note: values below the detection limit of 0.02 mg/L are reported as 0.01 mg/L.</attributeDefinition>
               <measurementScale>
                  <ratio>
                     <unit>
                        <standardUnit>milligramsPerLiter</standardUnit>
                     </unit>
                     <precision>0.001</precision>
                     <numericDomain>
                        <numberType>real</numberType>
                     </numericDomain>
                  </ratio>
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               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
            <attribute id="1240580800517">
               <attributeName>nh4</attributeName>
               <attributeDefinition>ammonium. Note: values below the detection limit of 0.005 mg/L are reported as 0.001 mg/L.</attributeDefinition>
               <measurementScale>
                  <ratio>
                     <unit>
                        <standardUnit>milligramsPerLiter</standardUnit>
                     </unit>
                     <precision>0.001</precision>
                     <numericDomain>
                        <numberType>real</numberType>
                     </numericDomain>
                  </ratio>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
            <attribute id="1240580800532">
               <attributeName>total.p</attributeName>
               <attributeDefinition>PO4 + dissolved organic P</attributeDefinition>
               <measurementScale>
                  <ratio>
                     <unit>
                        <standardUnit>microgramsPerLiter</standardUnit>
                     </unit>
                     <precision>0.1</precision>
                     <numericDomain>
                        <numberType>real</numberType>
                     </numericDomain>
                  </ratio>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
            <attribute id="1240580800548">
               <attributeName>po4</attributeName>
               <attributeDefinition>PO4. Note: values below the detection limit of 0.2 ug/L are reported as 0.1ug/L.</attributeDefinition>
               <measurementScale>
                  <ratio>
                     <unit>
                        <standardUnit>microgramsPerLiter</standardUnit>
                     </unit>
                     <precision>0.1</precision>
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               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
            <attribute id="1240580800564">
               <attributeName>bod</attributeName>
               <attributeDefinition>biological oxygen demand (mg O2/ L) following 5 day incubation</attributeDefinition>
               <measurementScale>
                  <ratio>
                     <unit>
                        <standardUnit>milligramsPerLiter</standardUnit>
                     </unit>
                     <precision>0.01</precision>
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               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
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            </attribute>
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               <attributeName>per.bioavailability</attributeName>
               <attributeDefinition>doc (as a function of BOD and DOC concentration)</attributeDefinition>
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                        <standardUnit>dimensionless</standardUnit>
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                     <precision>0.01</precision>
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               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
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            </attribute>
         </attributeList>
         <numberOfRecords>146</numberOfRecords>
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                  <url function="download">https://harvardforest.fas.harvard.edu/data/p04/hf043/hf043-02-ph-temp.csv</url>
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         </physical>
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                  </dateTime>
               </measurementScale>
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                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
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            <attribute id="1240580949470">
               <attributeName>temp</attributeName>
               <attributeDefinition>water temperature</attributeDefinition>
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                        <standardUnit>celsius</standardUnit>
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               <attributeDefinition>pH</attributeDefinition>
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               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
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         </attributeList>
         <numberOfRecords>970</numberOfRecords>
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         <entityDescription>CO2</entityDescription>
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                  </dateTime>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
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               <attributeName>co2</attributeName>
               <attributeDefinition>carbon dioxide</attributeDefinition>
               <measurementScale>
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                     <unit>
                        <customUnit>micromole</customUnit>
                     </unit>
                     <precision>0.01</precision>
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                        <numberType>real</numberType>
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                  </interval>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
         </attributeList>
         <numberOfRecords>961</numberOfRecords>
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                  </dateTime>
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               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
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               <attributeName>cdom</attributeName>
               <attributeDefinition>colored dissolved organic matter</attributeDefinition>
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                     <unit>
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                     <precision>0.001</precision>
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                        <numberType>real</numberType>
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                  </ratio>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
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               <attributeName>o2</attributeName>
               <attributeDefinition>dissolved oxygen</attributeDefinition>
               <measurementScale>
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               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
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               <attributeDefinition>water temperature</attributeDefinition>
               <measurementScale>
                  <interval>
                     <unit>
                        <standardUnit>celsius</standardUnit>
                     </unit>
                     <precision>0.001</precision>
                     <numericDomain>
                        <numberType>real</numberType>
                     </numericDomain>
                  </interval>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
            <attribute id="1240581227791">
               <attributeName>per.sat.o2</attributeName>
               <attributeDefinition>percent saturation of dissolved oxygen</attributeDefinition>
               <measurementScale>
                  <ratio>
                     <unit>
                        <standardUnit>dimensionless</standardUnit>
                     </unit>
                     <precision>0.001</precision>
                     <numericDomain>
                        <numberType>real</numberType>
                     </numericDomain>
                  </ratio>
               </measurementScale>
               <missingValueCode>
                  <code>NA</code>
                  <codeExplanation>missing value</codeExplanation>
               </missingValueCode>
            </attribute>
         </attributeList>
         <numberOfRecords>4565</numberOfRecords>
      </dataTable>
   </dataset>
   <additionalMetadata>
      <metadata>
         <additionalClassifications>
            <researchTopic>watershed</researchTopic>
            <studyType>short-term measurement</studyType>
         </additionalClassifications>
      </metadata>
   </additionalMetadata>
   <additionalMetadata>
      <metadata>
         <additionalLinks>
            <url name="Prospect Hill Hydrological Stations at Harvard Forest since 2005">https://harvardforest.fas.harvard.edu/exist/apps/datasets/showData.html?id=hf070</url>
         </additionalLinks>
      </metadata>
   </additionalMetadata>
   <additionalMetadata>
      <metadata>
         <unitList>
            <unit name="micromole"
                  unitType="amount"
                  id="micromole"
                  parentSI="mole"
                  multiplierToSI="0.000001"
                  constantToSI="0.0">
               <description>micromole</description>
            </unit>
         </unitList>
      </metadata>
   </additionalMetadata>
</eml:eml>
