Metadata record for data from ASAC Project 2784 See the link below for public details on this project. This project utilised an existing 55 year model reanalysis (SODA) - so no new models were developed. The methodologies/data used are described in the referenced publications. Modelling investigations of the shoaling of iron-rich upper circumpolar deep water (UCDW) and its role in the regulation of primary production at 60-65S. Taken from the project application: We intend to utilise a number of existing data sources to study the factors leading to spatiotemporal variability in the upwelling of iron-rich UCDW in the 60-65S zone, which, as discussed above, seems critical to regional ecosystem function, and the carbon and sulphur budgets of the SO. As sea-ice extent appears to have declined in the Southern Ocean since the 1950s (Curran et al., 2003) it will also be extremely interesting to examine whether this has had any affect on the upwelling of the UCDW. Given the restricted spatial domain of in situ field data in the Southern Ocean, satellite products provide us with one of the few means to investigate coherent variability over large spatial and temporal scales. This study takes advantage of our previous AAS funded work (Projects: 2584, 2319), where we have gained considerable experience in the coupling of biogeochemical and climate models and where we have already assembled satellite data sets on wind speed, sea-ice, SST, aerosols and chlorophyll-a concentration. This previous experience will allow us to examine the relationship between the physical forcings, the dynamics of the UCDW and the biological response on seasonal and interannual timescales over the period 1950-2000. The key scientific questions we seek to answer include: - What is the range of interannual and interdecadal variability in upwelling of the UCDW and how does this relate to variability in primary production? - Is there a connection between interannual/decadal variability in sea-ice extent and the strength or location of upwelling of UCDW and hence the character of regional primary production? - Is there a relation between the seasonal production of DMS and associated S-aerosols and the dynamics of UCDW? Details from previous years are available for download from the provided URL. Taken from the 2009-2010 Progress Report: Progress against objectives: This three-year project has been investigating the nexus between the large-scale meridional circulation patterns in the SO, in particular UCDW upwelling, and concomitant iron delivery to surface waters and the phytoplankton. Key Scientific Questions to be considered by the project What is the range of interannual and inter-decadal variability in upwelling of the UCDW and how does this relate to variability in primary production? This study initially focussed on the Australian region of the Southern Ocean (110-160 degrees S, 40-70 degrees E) and the physical oceanographic data for the project came from monthly Simple Ocean Data Assimilation (SODA) reanalysis data, which covers the period 1958-2007 over the global ocean. Decadal-scale trends in upper ocean structure and meridional circulation were analysed, including the upwelling of nutrient-rich UCDW, and these results were initially documented in presentation (3) below and will shortly be published in publication (1) listed below. The project identified UCDW in SODA using temperature and density criteria and, using this, a number of variables were developed to characterise UCDW and its upwelling: UCDW vertical velocity, temperature, density and salinity, UCDW top depth (the shallowest depth at which UCDW is found) and UCDW southern-most position. Climatological values were found for each of the 5-degree strips in the sector and, in addition, trends were found over the period 1958-2005. Later work involved comparing these results with those of two more Southern Ocean sectors - one in the Pacific (130-80 degrees W) and one in the Indian Ocean (20-60 degrees E). These results were presented at the AMOS conference in January 2010 (see Presentation (1) below) and are also the subject of a paper in the Proceedings of that conference (see Publication (2) below). It was found that during 1958-2005: (1) UCDW top depth varies seasonally, peaking in March, and displays considerable interannual variability; (2) Climatological properties for UCDW variables such as temperature, vertical velocity and upwelling depth vary between the three ocean sectors, as do trends (1958-2005) in the UCDW variables; (3) UCDW vertical velocity (ie. upwelling) appears to be increasing with time in most intermediate and deep waters of the three ocean sectors; (4) UCDW temperature is increasing in intermediate waters in the Pacific sector, at all depths in the Indian sector and at shallow depths in the Australian sector, but is decreasing in intermediate and deep waters in the Australian sector; (5) UCDW southern-most position is moving south in the Australian and Pacific sectors; (6) UCDW is upwelling closer to the surface in the Australian and Indian sectors and, in the case of the Australian sector, this translates into an increase in the number of times that UCDW can be detected in the mixed layer (a finding of possible importance for primary production); (7) UCDW trends in the Australian sector do not appear to be affected by trends in the winds, but by forcings acting on longer than decadal time-scales. This is not the case, however, for the other two sectors, leading to the speculation that these variables may be affected by the re-entry into UCDW of recirculated waters from the Indian and Pacific Oceans, which may themselves be affected by winds. (8) The Australian sector of the SO has been shown to have its own unique characteristics, distinct from either the Pacific or Indian sectors. More recent work has involved looking at the initial Australian sector considered above, over the period of the high resolution satellite data capture era (1997-2007), with the aim of using satellite data on chlorophyll a (chl a), sea-ice concentration and photosynthetically active radiation (PAR), as well as modelled data for primary production (PP), in addition to the reanalysis data, to look at factors that influence chl a and PP over that time period. Initial work was presented at the AMOS conference in January 2009 (see Presentation (2) below) and final work is reported in Publication (3) listed below, which is almost ready for submission. It was found that in the Australian sector during 1997-2007: (1) The most important controls on chl a in spring are sea-ice concentration and PAR in the southern-most zones (and mixed layer depth, SST, stratification and PAR in zones further north); (2) The situation is more complex in summer, especially in the southern-most zones (the areas of highest production, excluding the most northerly zone near Tasmania). In particular, in the 60-65 degrees S zone in summer, a variety of inter-acting controls affect chl a (and PP), including SST, stratification and UCDW top depth; (3) The number of times that UCDW is detected in the mixed layer is decreasing in summer during 1997-2007; (4) It is difficult to identify trends that are statistically significant over such a short time period and trends that are found are often opposite in sign to those for 1958-2005 and up to an order of magnitude larger. Thus care needs to be taken with trends found for chl a, PP and hydrodynamic variables over the short period of the satellite era, since there is a large range of such ten-year trends in the period 1958-2005. Is there a connection between interannual/decadal variability in sea-ice extent and the strength or location of upwelling of UCDW and hence the character of regional primary production? Given that UCDW upwells south of the Polar Front and no further south than the Southern Boundary of the ACC (approximately 65 degrees S in this sector), then UCDW, as identified here in its pure form, is not able to affect the 65-70 degrees S zone (although this is possible in its modified form, which is not studied here). It was found that, for the period 1997-2007 in the Australian sector of the SO, the southern-most position of UCDW is not correlated with sea-ice concentration, but that there are weak (90% level) correlations in 60-65 degrees S between UCDW top depth and sea-ice concentration in autumn (positive), the temperature of UCDW and sea-ice concentration in summer (positive) and northward Ekman transport and sea-ice concentration in summer (negative). It was found that, for 1997-2007 in the Australian sector of the SO, sea-ice concentration has a significant (inverse) relationship with chl a and PP in 60-70 degrees S in spring and 65-70 degrees S in summer. In addition, UCDW top depth and northward Ekman transport (ie. how quickly the UCDW nutrients are transported northwards and away from the zone) have a minor effect on chl a in 60-65 degrees S in summer.

Overview of the project and objectives: To investigate whether the Nitrogen - Silicon - Carbon biogeochemical system functions in the Antarctic Marginal Ice Zone and shows spatial variability possibly induced by varying availability of Fe and other parameters in the region. This toolbox is part of project 4051 - samples were taken (1) on the same sea-ice site or very close than the one used for Trace Metal sampling; (2) via Trace Metal Rosette TMR; (3) via Conductivity Temperature and Depth CTD Rosette. It is also part of project 4073 since some intercalibration studies were conducted in collaboration with the primary production team. Three main tools were used which can be either independently or intricately studied. For this reason the complete set of sampling done for this stable isotope toolbox is summarized in one excel file which is duplicated and attached to three child metadata records. Same reasoning for raw data acquired on boar and on field information. This parent metadata record has thus three child metadata records. Each of the child metadata files explain individually the different approaches which were treated together by the same team to resolve the main question of sea-ice biogeochemical system functioning via the use of stable isotope ratio tools. The details of each are in the respective metadata records. The data are attached to this metadata record. METADATA FILES are: - 13C, 15N, 30Si in-situ incubation experiments during SIPEX 2 - Nitrogen and oxygen isotopic composition of nitrate during SIPEX 2 - Delta13C signal of brassicasterol and cholesterol in the Antarctic Sea-ice / Is there particulate barium in sea-ice?

Antarctic sea ice is known to store key micronutrients, such as iron, as well as a suite of less studied trace metals in winter which are rapidly released in spring. This stimulates ice edge phytoplankton blooms which drive the biological removal of climatically-important gases like carbon dioxide. By linking the distribution of iron and other trace elements to the cycles of carbon, nitrogen and silicon in the sea ice zone in spring, this project will identify their biogeochemical roles in the seasonal ice zone and how this may change with predicted climate-driven perturbations. All sampling bottles and equipment were decontaminated using trace metal clean techniques. Care was taken at each site to select level ice with homogeneous snow thickness. At all the stations, the same sampling procedure has been used : Firstly, snow was collected using acid cleaned low density polyethylene (LDPE) shovels and transferred into acid-cleaned 3.8 l LDPE containers (Nalgene). Snow collected is analysed for temperature, salinity, nutrients, unfiltered and filtered metals. Snow thickness is recorded with a ruler. Ice cores were collected using a noncontaminating, electropolished, stainless steel sea ice corer (140 mm internal diameter, Lichtert Industry, Belgium) driven by an electric power drill. Ice cores were collected about 10 cm away from each other to minimise between-core heterogeneity. A first core is dedicated to the temperature, salinity and Chlorophyll a (Chla). To record temperature, a temperature probe (Testo, plus or minus 0.1 degrees C accuracy) was inserted in holes freshly drilled along the core every 5 to 10 cm, depending on its length. Bulk salinity was measured for melted ice sections and for brines using a YSI incorporated Model 30 conductivity meter. Chla is processed on board using a 10 AU fluorometer (turner Designs, Sunnyvale California). All those data, read from the screens instruments are directly inserted in the spreadsheet 'Notebook SIPEX-2' in the '4051 Lannuzel' folder. The total length of this core is cut in sections of 7 cm. The second core is dedicated to the POC/PON (Particulate Organic Carbon/ Particulate Organic Nitrogen), DOC (Dissolved Organic Carbon) and nutrients. Six sections of 7 cm are taken from this core. The six sections were chosen so that two top, two intermediate and two basal sections. Two cores are taken for the trace metal analysis. Those cores are directly triple bagged in plastic bags (the inner one is milli-Q washed) and frozen at -20 degrees C until analysis at the laboratory. Brine samples were collected by drainage from "sack holes". Brines and under ice seawater (~1 m deep) were collected in 1 l Nalgene LDPE bottles using an insulated peristaltic pump and acid cleaned C-flex tubing (Cole Palmer). All samples were then transported to the ship as quickly as possible to prevent further freezing. Those samples are used to analyse unfiltered and filtered metals, Chla, POC/PON, nutrients and DOC. Filtration for filtered metals is done on board using a peristaltic pump and a 0.2 micron cartridge filter. All the unfiltered and filtered metals collected are acidified (2 ppt HCl seastar) and stored at room temperature until analysis at the laboratory. Nutrients, DOC and filters for POC/PON are frozen at -20 degrees C until analysis. Chla filtrations and analysis are done on board. Auxiliary cores/brines/underlying seawater were also collected for Caitlin Gionfriddo (caitlingio@gmail.com, Uni. Melbourne) for total mercury (Hg) and methyl-Hg. Also included in this dataset are typed field notes.

Overview of the project and objectives: Assessing the contribution of the different N substrates to the primary production process, such as the biogenic silica production and dissolution in the Antarctic sea-ice provides a means to understand the biogeochemical system functioning. In such a semi closed-type system, assess incorporation rates of HCO3-, NO3-, NH4+, SiOH4, BSi dissolution, nitrification, C-release in close-by ice-cores (3 ice-cores dedicated to (i) 13C-assimilation + 15NH4+ uptake rate, (ii) 13C-assimilation + 15NO3- uptake rate and nitrification, (iii) Biogenic silica production and dissolution via 30Si isotope tool) will allow improving the knowledge of system functioning. This is also closely linked to the thematic of iron availability since these experiments are done close to / on the Trace Metal site allowing us to hopefully propose a relatively complete image of biogeochemical activity and relationship with trace metals on this site. Methodology and sampling strategy: Most of the time we worked close to / directly on the Trace Metal site following precautions concerning TM sampling (clean suits etc.). When we worked close to the TM site, precautions were not such important because we don't need the same drastic precautions for our own sampling. We work together because we want to propose a set of data which helps to characterize the system of functioning in close relation with TM availability (for that, sampling location have to be as close as possible). 14C and 13C-incubation experiment intercalibration work were conducted on the Biosite (different place than TM site except for station 7) Incubation experiment samples are analyzed via (1) Elemental Analyzer - Isotope Ratio Mass Spectrometer (EA-IRMS) for carbon and nitrogen (VUB, Brussels, Belgium); (2) High Resolution Inductively Coupled Mass Spectrometer (HR-ICPMS) for silicon (RMCA, Brussels, Belgium).

Data were collected during the 1997-1998 austral summer on voyages by the Aurora Australis and Southern Surveyor. Taken from the abstract of the referenced paper: Oceanographic processes in the subantarctic region contribute crucially to the physical and biogeochemical aspects of the global climate system. To explore and quantify these contributions, the Antarctic Cooperative Research Centre (CRC) organised the SAZ Project, a multidisciplinary, multiship investigation carried out south of Australia in the austral summer of 1997-1998. Here we present a brief overview of the SAZ Project and some of its major results, as detailed in the 16 papers that follow in this special section. The Southern Ocean plays an important role in the global oceanic overturning circulation and its influence on the carbon dioxide contents of the atmosphere. Deep waters upwelled to the surface are rich in nutrients and carbon dioxide. Air-sea interaction modifies the upwelled deep waters to form bottom, intermediate, and mode waters, which transport freshwater, oxygen, and carbon dioxide into the ocean interior. The overall effect on atmospheric carbon dioxide is a balance between outgassing from upwelled deep waters and uptake via both dissolution in newly formed waters (sometimes referred to as the solubility pump) and the transport of photosynthetically formed organic carbon to depth in settling particles (referred to as the biological pump). Determining the variations in the overturning circulation and the associated carbon fluxes in the past and their response to increased anthropogenic emissions of carbon dioxide in the future is essential to a full understanding of the controls on global climate. At present the upwelled nutrients are incompletely used. Low light in deep wind-mixed surface layers, lack of the micronutrient iron, and other factors restrict phtyoplankton production so that Southern Ocean surface waters represent the largest high-nutrient, low chlorophyll (HNLC) region in the world.

Oceanographic processes in the subantarctic region contribute crucially to the physical and biogeochemical aspects of the global climate system. To explore and quantify these contributions, the Antarctic Cooperative Research Centre (CRC) organised the SAZ Project, a multidisciplinary, multiship investigation carried out south of Australia in the austral summer of 1997-1998. Taken from the abstracts of the referenced papers: The development of a semi-automated batch HG-AFS method for the shipboard determination of As(III), As(V),MMA and DMA is described. Procedures in the analytical sequence including addition of NaBH4 to samples, cooling and heating the U-trap used for pre-concentration and separation of the arsines, and logging the AFS output are automated. Overall control of the automated tasks into a logical analytical sequence is achieved using a commercially available data acquisition and control package, workbenchmac(TM). Further modifications required for the method to be adapted to shipboard use, including the use of a hydrogen generator, are also detailed. This method shows a number of advantages over a previously reported manual HG-AFS method including, shorter sample throughput time, increased precision and most significantly, ease of use under shipboard conditions. The semi-automated method was operated on the RSV Aurora Australis during a Southern Ocean voyage in March 1998. Arsenic measurements from a surface transect between 42 and 55 degrees S along 141 degrees 30 minutes E, are presented. Application of the method to more routine laboratory use is also discussed. Distribution of the arsenic species total inorganic arsenic [As(V+III)], arsenite [As(III)], monomethyl arsenic(MMA), andd dimethyl arsenic (DMA) was studied in the Subantarctic Zone (SAZ) of the Southern Ocean, south of Australia, during the austral autumn (March 1998). As (V) was the dominant arsenic species in both vertical profiles and surface waters along the meridional transect 42-55 degrees S, 141 degrees 30' E. It was also the only species observed at depths greater than 600 m. Concentrations of the reduced arsenic species (As(III), MMA, and DMA) were low in these waters compared with other oceanic sites with similar concentrations of chlorophyl a. As(III) concentrations could not be reliably quantified at any sites (less than 0.04 nM). The greatest conversion of As(V) to "biological" species was found at the surface in the Subtropical Convergence Zone(2.5%) and decreased heading southward to 1% in the Polar Front (PF). While the decline in methyl arsenic concentrations was broadly associated with water temperature and measures of biological production, slightly different trends were found in the SAZ and PF. North of the Subantarctic Front (SAF), methyl arsenic concentrations were well correlated with water temperature, while south of the front, no such relation existed. In addition, the ratio DMA/MMA increased south of the SAF, associated with a change in the microalgal community composition. Low water temperature, phosphate replete conditions, and low biological productivity in the Southern Ocean all contribute to the concentrations of biologically produced arsenic species in this region being among the lowest reported for oceanic waters.

Data were collected during the 1997-1998 austral summer on voyages by the Aurora Australis and Southern Surveyor. Oceanographic processes in the subantarctic region contribute crucially to the physical and biogeochemical aspects of the global climate system. To explore and quantify these contributions, the Antarctic Cooperative Research Centre (CRC) organised the SAZ Project, a multidisciplinary, multiship investigation carried out south of Australia in the austral summer of 1997-1998. Ammonia data were collected by Ros Watson (and provided by Tom Trull), and as of 2012, are unpublished.

Oceanographic processes in the subantarctic region contribute crucially to the physical and biogeochemical aspects of the global climate system. To explore and quantify these contributions, the Antarctic Cooperative Research Centre (CRC) organised the SAZ Project, a multidisciplinary, multiship investigation carried out south of Australia in the austral summer of 1997-1998. Taken from the abstracts of the referenced papers: In March 1998 we measured iron in the upper water column and conducted iron- and nutrient-enrichment bottle-incubation experiments in the open-ocean Subantarctic region southwest of Tasmania, Australia. In the Subtropical Convergence Zone (~42 degrees S, 142 degrees E), silicic acid concentrations were low (less than 1.5 micro-M) in the upper water column, whereas pronounced vertical gradients in dissolved iron concentration (0.12-0.84 nM) were observed, presumably reflecting the interleaving of Subtropical and Subantarctic waters, and mineral aerosol input. Results of a bottle-incubation experiment performed at this location indicate that phytoplankton growth rates were limited by iron deficiency within the iron-poor layer of the euphotic zone. In the Subantarctic water mass (-46.8 degrees S, 142 degrees E), low concentrations of dissolved iron (0.05-0.11 nM) and silicic acid (less than 1 micro-M) were measured throughout the upper water column, and our experimental results indicate that algal growth was limited by iron deficiency. These observations suggest that availability of dissolved iron is a primary factor limiting phytoplankton growth over much of the Subantarctic Southern Ocean in the late summer and autumn. The importance of resource limitation in controlling bacterial growth in the high-nutrient, low-chlorophyll (HNLC) region of the Southern Ocean was experimentally determined during February and March 1998. Organic- and inorganic-nutrient enrichment experiments were performed between 42 degrees S and 55 degrees S along 141 degrees E. Bacterial abundance, mean cell volume, and [3H]thymidine and [3H]leucine incorporation were measured during 4- to 5-day incubations. Bacterial biomass, production, and rates of growth all responded to organic enrichments in three of the four experiments. These results indicate that bacterial growth was constrained primarily by the availability of dissolved organic matter. Bacterial growth in the subtropical front, subantarctic zone, and subantarctic front responded most favourably to additions of dissolved free amino acids or glucose plus ammonium. Bacterial growth in these regions may be limited by input of both organic matter and reduced nitrogen. Unlike similar experimental results in other HNLC regions (subarctic and equatorial Pacific), growth stimulation of bacteria in the Southern Ocean resulted in significant biomass accumulation, apparently by stimulating bacterial growth in excess of removal processes. Bacterial growth was relatively unchanged by additions of iron alone; however, additions of glucose plus iron resulted in substantial increases in rates of bacterial growth and biomass accumulation. These results imply that bacterial growth efficiency and nitrogen utilisation may be partly constrained by iron availability in the HNLC Southern Ocean. The download file also contains three excel spreadsheets of iron data from the project. The file Sedwick_A9706_Fe_data contains water-column dissolved Fe and total-dissolvable Fe data from cruise A9706, which is presented in Sedwick et al. (1999) and Sedwick et al. (2008). The files Sedwick_A9706_ProcessStn1_Exp_data and Sedwick_A9706_ProcessStn2_Exp_data present data from shipboard experiments conducted during cruise A9706 at Process Stations 1 and 2, respectively, as reported in Sedwick et al. (1999).

Oceanographic processes in the subantarctic region contribute crucially to the physical and biogeochemical aspects of the global climate system. To explore and quantify these contributions, the Antarctic Cooperative Research Centre (CRC) organised the SAZ Project, a multidisciplinary, multiship investigation carried out south of Australia in the austral summer of 1997-1998. Taken from the abstracts of the referenced paper: We developed and applied a one-dimensional (z) biophysical model to the Subantarctic Zone (SAZ) and the Polar Frontal Zone (PFZ) to simulate seasonal phosphate export production and resupply. The physical component of our model was capable of reproducing the observed seasonal amplitude of sea surface temperature and mixed layer depth. In the biological component of the model we used incident light, mixed layer depth, phosphate availability, and estimates of phytoplankton biomass from the Sea-viewing Wide Field-of-view Sensor to determine production and tuned the model to reproduce the observed seasonal cycle of phosphate. We carried out a series of sensitivity studies, taking into account uncertainties in both physical fields and biological formulations (including potential influence of iron limitation), which led to several robust conclusions (as represented by the ranges below). The major growing season contributed 66-76% of the annual export production in both regions. The simulated annual export production was significantly higher in the PZF (68-83 mmol P m-2) than in the SAZ (52-61 mmol P m-2) despite the PFZ's having lower seasonal nutrient depletion. The higher export production in the PFZ was due to its greater resupply of phosphate to the upper ocean during the September to March period (27-37 mmol P m-2) relative to that in the SAZ (8-15 mmol P m-2). Hence seasonal nutrient depletion was a better estimate of seasonal export production in the SAZ, as demonstrated by its higher ratio of seasonal depletion/export (64-78%) relative to that in the PFZ (34-47%). In the SAZ, vertical mixing was the dominant mechanism for supplying phosphate to the euphotic zone, whereas in the PFZ, vertical mixing supplied only 37% of the phosphate to the euphotic zone, whereas in the PFZ, vertical mixing supplied only 37% of the phosphate to the euphotic zone and horizontal transport supplied the remaining 63%.

Sampling was conducted according to GEOTRACES protocols. Samples for trace element analyses, including dissolved iron (dFe), were filtered through acid-cleaned 0.2 um cartridge filters (Pall Acropak) under constant airflow from several ISO class 5 HEPA units. All plastic ware was acid-cleaned prior to use, following GEOTRACES protocols. Samples were collected into low-density polyethylene (LDPE) bottles, acidified immediately to pH 1.7 with Seastar Baseline hydrochloric acid (HCl), double-bagged and stored at room temperature until analysis on shore. Samples for dFe analysis were pre-concentrated offline (factor 40) on a SeaFAST S2 pico (ESI, Elemental Scientific, USA) flow injection system with a Nobias Chelate-PA1 column. Samples were eluted from the column in 10% distilled nitric acid (HNO3), with calibration based on the method of standard additions in seawater (made using multi-element standards in a 10% HNO3 matrix, rather than an HCl matrix). Pre-concentrated samples were analysed using Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS, Thermo Fisher Scientific, Inc.). Data were blank-corrected by subtracting an average acidified milli-Q blank that was treated similarly to the samples. The dFe detection limit for a given analysis run on the SeaFAST/SF-ICP-MS was calculated as 3 x standard deviation of the milli-Q blank on that run. Detection limits ranged from 0.016 to 0.067 nmol kg-1, with a median of 0.026 nmol kg-1 (n=12). GEOTRACES reference materials were analyzed along with samples and results were in good agreement with consensus values: SAFe D1 was measured at 0.69 +/- 0.05 nmol kg-1 (n=7; consensus value = 0.67 +/- 0.04 nmol kg-1) and GD was measured at 1.02 +/- 0.01 nmol kg-1 (n=6; consensus value = 1.00 +/- 0.1 nmol kg-1). Comments regarding the data spreadsheet: NaN = no sample dFe QC flags: 1 = high confidence in data quality 2 = detection limit 3 = low confidence in data quality detection limits: dFe data that were below the daily detection limit were replaced with the respective detection limit. They are flagged with the number 2 in the dFe QC flag column.