the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Technical note: Efficiency of various evaporation barriers for use in automated water samplers for subsequent water isotope analysis
Abstract. High temporal and spatial resolution water sampling of stream water or precipitation for subsequent stable water isotope analysis (δ2H and δ18O) is commonly conducted with self-made or commercial automated samplers. However, prolonged storage of water samples in open bottles inside autosamplers can lead to isotopic alterations caused by evaporative fractionation and vapor mixing.
In this study, we tested the effectiveness of different evaporation barriers—dip-in tubes, ball valves, and siphons—under controlled laboratory conditions. Experiments were conducted using glass bottles with varying filling levels (50 mL to 250 mL in 250 mL bottles) and exposure times of up to 52 days. Our results demonstrate that all tested barriers effectively reduce isotopic alterations. Among these, the dip-in tube emerged as the simplest and most efficient solution, reliably preserving isotopic data even over extended storage durations. We also observed isotopic differences between the water in the dip-in tube and the main bottle. This phenomenon becomes particularly relevant when sample volumes are very low, as water from the dip-in tube may influence the overall isotopic composition of the sample. This finding highlights the need for careful consideration of bottle design, funnel size and sample handling, especially with low water volumes.
These findings provide valuable insights for the design of cost-effective, automated water sampling systems for stable isotope applications, emphasizing the importance of evaporation barriers to ensure reliable and accurate isotopic analyses.
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RC1: 'Comment on egusphere-2025-272', Anonymous Referee #1, 11 Mar 2025
The Technical note: Efficiency of various evaporation barriers for use in automated water samplers for subsequent water isotope analysis by Mueller, Pekarev, and Knoeller evaluate in two experiments evaporation minimizing closers.
The manuscript overall well-written and clear, requiring only minor clarifications (detailed below). It makes a valuable contribution to water sampling best practices by presenting novel findings on evaporation effects, particularly with different closure types. This builds upon existing research and helps to design optimal water samplers for stable isotope analysis.Minor points:
- To better present the difference between different closers, the authors should include a Z-score to compare different closers.
- A more detailed comparison with varying tube-dip diameters and d-exe used and found by other studies, e.g., Prechsel et al., Carton et al., and Natali et al. 2024, should be performed to potentially see the effect of different diameters of tube-dips and evaporate/ D-exe.
- To make consistent with the literature, use tube-dip instead of dip in
- L38-> Keep general or include other manufacturers.
- L40-> "in" or ratios of water...?
- 55-> "Iaea" capital letters and make manuscript consistent
- L84 -> I'm not sure if this is a research gap. It should be based on the scientific gap, not on a company's collaboration and test. Although the study was in collaboration, it is better to remove the company name from the main text and refer to it only in the acknowledgements.
This will allow to see the technical note in a broader view and application, which is more beneficial for the community. - L100-> The experiments were unclear from the text; only after seeing Figure 3, it became clear. Therefore, state here as text as in Figure 3 that Experiment 1 consisted of bottles with different caps, such as Ref closed ref open siphon, etc.
What was the goal of the experiment? Experiment 1 tested the syphon as an evaporation barrier. - L106-> specify what temperature and humidity. In our lab in the tropics this could affect the evaporation and isotopic composition compared to other climate zones.
- L110-> Mention already here what the purpose of the experiment 1 and 2 were?
- L111-> "15 m long hose” Provide diameter
- L144-> It seems in the open bottle, there was evaporation. Include.
- L145 ->This sentence is not clear. Which method and what was challenging? Rephrase.
- L147-> 151 and 153 "mean = 0.12 ...." units are missing.
- Figure 3 -> Consider using a log scale for the y-axis.
- L206-> move to method
- L223 ->max or min? Double-check
- Why in experiment 2 the evaporation in % was not shown?
- Figure 8 ->evaporation lines? Is it the same axis interval? S
- Figure 9 -> Craig-Gordon evaporation lines?
Citation: https://doi.org/10.5194/egusphere-2025-272-RC1 -
RC2: 'Comment on egusphere-2025-272', Anonymous Referee #2, 19 Mar 2025
The authors tested several different inlet designs of bottles designed for automated natural rainfall water sampling with the aim of preserving the samples’ isotopic composition for up to several weeks prior to lab-based analysis. This is an attempt to optimize the design first described by Gröning et al. (2012). Ultimately, the authors found the original design to be superior compared to the tested alternatives. Nonetheless, the findings are of interest for readers of HESS and I recommend publication after minor revision.
General comments:
The authors refer to various climatic conditions for which users of automated sampling systems should carefully choose between the available options. However, the only “climatic” scenario tested in this study was ‘stable (room-)temperature in the lab’. There was no other scenario tested in which the ball valve and/or the siphon could/would have been advantageous. In addition, the proposed solution for dealing with enrichment of heavy isotopes inside the dip-in tube is not applicable in (to be expected) cases of sequential rainfall. The authors only tested a scenario where they filled the bottles to their final filling level at the beginning of the respective observation periods. This does not reflect natural conditions, under which sequential rainfall during the selected observation period would flush out the dip-in water. I ask the authors to expand on this in the discussion.
Specific comments:
L16 (and throughout the manuscript): “water stable isotope”, not “stable water isotope”
L19: instead of vapor mixing, I think the physical process is rather unidirectional diffusion caused by vapor pressure gradients
L27: You mention funnel size in the abstract but you do not investigate/discuss this aspect in the manuscript
L33: “long and large” = “long-term and large-scale”?
L37: Please provide references for this statement
L48: “isotope”, not “isotopic”
L53: “sold”, not “sell”
L55 and elsewhere: “IAEA” (all caps), not “Iaea”
L64: “created”, not “was creating”
L75: 'high sediment loads and microbial activity' is not a problem addressed in this study. Why do you unnecessarily lead the readers in this direction?
L80: was aridity the problem or rather limited access to the sampling site?
L81: what do you mean by “sample loss” other than evaporation?
L86: if “use in various climatic regions” was the goal, then why did you not specifically test various conditions?
L105: instead of “ranged between” + the list of settings, I’d recommend “was xx, yy or zz mL”; also: “5, 7, 20, or 21 days”
L108: “designed”, not “design”
L112: “or”, not “and” (13, 26, 39 or 52 days)
L117: why was that an 'optimal scenario'? Wouldn’t low temperatures like in refrigerators – the standard place for sample storage in all labs I know – be much better to reduce evaporation? Or high relative humidity to prevent/reduce vapor pressure gradients?
L121f: Please insert “part” or “panel” before “A” and “B”, also: delete “evaporation barriers” and parenthesis and insert “as evaporation barriers” after “tube”
L126: “floating”, not “swimming”
L130: delete “liquid” or insert “water” after “liquid”
L131: please define abbreviations upon first appearance (you do so in L133f)
L146ff: please add units to mean and SD
L147: please insert “relative” before “volume”
L152: why was the mean weight loss negative (-1.14)?
L153: for me, "contamination" refers to the addition of unwanted substances. Maybe better “compromising” or “flawing”?
L159: please define the null hypothesis
L162: please insert “a siphon and” after “only”
L164 (Figure 3): Where do I find data for dip-in only (referred to in L147)?
L172: Deuterium excess is not the deviation from the GMWL, as a value of 0 does not mean ‘no deviation’ but a deviation of 10 (as you correctly explain in L175f). Also, not only the δ2H-H2O value is relevant but also the δ18O-H2O. I’d suggest something like: “Deuterium excess refers to the vertical deviation of water isotope data in permill from the GMWL in dual isotope space. It provides…”
L174: “variable”, not “parameter”
L175: “Isotope data plotting” instead of “water”
L176: insert “value” after “excess”
L177: please insert “as reference for“ and “values” after “GMWL” and “excess”, respectively.
L178: please rephrase. Maybe: “Deuterium excess values from experiment 1 indicate the highest…”?
L180: “highest” or rather “lowest”?
L182: please insert “”of storage”, “color and” and “, respectively” after “duration”, “point” and “size”, respectively (if that is what you mean).
L191: please insert “measurements” after “isotope(s)”
L196ff: I'm afraid, sequential rainfall will make this effort pointless. Does this mean that siphons are only useful for sampling single rainfall events (if at all)?
L205 (and elsewhere): be consistent: dip-in, not Dip-in
L211: delete “however” as the statements before and after do not contradict
L214f: Please move this sentence to the method section and explain how dip-in water was sampled. What was the volume of dip-in water? What was the height of the water column inside the dip-in tube?
L216: 54 days? Elsewhere in the MS you state 52 days as maximum storage duration. Typo?; also: consider inserting “2” after “with”
L218: please delete “the results of the” and insert “data” or “values” after “excess”
L219: please insert “data” or “values” after “excess”
L221: not largest, but lowest d-excess values were observed, right?
L222: min, not max
L224: please insert “d-excess values of” after “only” and “GMWL by more than the” before “measurement”
L225f: the slope of an evaporation line is a function of relative humidity (Gonfiantini, R., 1986, Environmental Isotopes in Lake Studies. In P. Fritz, & J.-Ch. Fontes (Eds.), Handbook of Environmental Isotope Geochemistry (pp. 113-168)) with greater slopes occurring under more humid conditions. Potentially, the layer of quasi-saturated air above the water surface inside the open bottle was thick enough to mimic saturation and cause the slope of the evaporation line to be very close to eight – although this contradicts the case of dip-in tube and siphon(?)
L228 and L232: please insert “values” or “signatures” or equivalent after “isotope(s)”
L258: How would you determine the appropriate bottle size? I assume, it is a function of expected rainfall depth and collector funnel area(?) Please share your thoughts on this and ideally make a suggestion
L260: I think this sentence should appear before the statement in L256 where you already refer to a part of Figure 9.
L264: I seem to be unable to find the arrows in Fig. 9B
L283 and L286: see comment to L19
L287: please insert “combined” or equivalent after “dip-in tube” to clarify that the pressure compensation tube (and not the dip-in tube) was long. Generally, this sentence seems to suggest that you tested alternatives to the long tube, which you have not. Please consider rephrasing
L291: why are these conditions more likely to cause differences that are more evident? I think that low (stable) temperatures and high (stable) humidity would rather reduce this effect, as low vapor pressure gradients would induce only little evaporation.
L295: under what circumstances would you recommend complicating a setup by adding ball valves and siphons? Imho, your data (and the conditions under which you collected them) do not give a hint in this regard.
L300: please elaborate on this and be more specific about “specific” (here or in the discussion). What barriers are recommended under what conditions and why? Don’t your data suggest that 'dip-in tube only' is the simplest (construction-wise) and best (isotope-wise) solution?Citation: https://doi.org/10.5194/egusphere-2025-272-RC2 -
RC3: 'Comment on egusphere-2025-272', Anonymous Referee #3, 24 Mar 2025
General comments:
In the manuscript by Mueller et al. the authors present the effectiveness of three different evaporation barriers under controlled laboratory conditions, whereby the dip-in tube is a well-established method (Groening et al., 2012) for sampling of precipitation water for stable isotope analysis.
The two experiments they carried out were conducted with glass bottles of different sizes (50-250 mL) and exposure times from five to 52 days.
Overall, the manuscript is nicely written and well structured. The topic will be of interest for the readers of HESS and can be recommended for publication after minor revisions.However, the authors state that their goal is to create a system for use in various climatic regions (L. 86). This stated goal is a bit misleading, as all experiments were conducted explicitly under constant conditions, only (L. 116). I suggest rephrasing the statement in the introduction.
Apart from that I have the following specific and technical comments.
Specific Comments:
L. 30: and throughout the manuscript ‘water stable isotopes’ not ‘stable water isotopes’
L. 33: ‘…long and large interference to the gas phase…’ be a bit more precise and specific. I guess you mean exposition, diffusive exchange with ambient atmosphere, etc.
L. 37: REFs missing
L. 48 and throughout: check the order of your references (oldest – newest)
L. 53 and throughout: check references that are included in the text e.g., ‘…published by Gröning et al. (2012)…’ instead of ‘…published by (Gröning et al., 2012)’
L. 55: introduce ‘IAEA’ here, not in L. 57. Throughout: ‘IAEA’ in capitals.
L. 76: Please add REFs here and add a sentence to the discussion or delete this statement, as it’s not your main topic.
L. 81: what do you mean with ‘sample loss’?
L. 97-100: The first setup was used for the first experiment only. Please rephrase, to make clearer that ‘setup’ and ‘experiment’ is used synonymously here.
L. 146 ff.: Most of the ‘Mean’ values you are describing here are negative in the Figure. Please check.
L. 147: the numbers given here (‘Mean’ and ‘SD’) are from the ‘Siphon&Dip-In’ in Fig 3. Please check and change in either the text or the figure.
L. 159: Where is the null hypothesis mentioned/ defined?
L. 172: Deuterium-Excess is not defined as the deviation from the GMWL. Please rephrase to be more precise.
L. 174: D-Ex can be used to identify ‘isotope fractionation’, not ‘water fractionation’.
L. 177: ‘The GMWL for deuterium excess…’ there is no GMWL for deuterium excess, please rephrase.
L. 180 and L. 221: It is the ‘lowest’, not ‘highest’ deuterium excess, when greatest extent of evaporation is indicated.
L. 182: this sentence seems to be incomplete, please insert ‘of storage’ after ‘The duration…’ and then it’s ‘…symbol color and point size, respectively…’
L. 214-215: This detail of the sampling procedure is missing in the Methods and Materials-section.
L. 264: which arrows, can’t see any in Fig 9B?
L. 292-293: This detail of the sampling procedure is missing in the Methods and Materials-section.
L. 296: ‘…can also be used’ Do you mean equally recommended as the dip-in?Fig 9: I suggest using a color scheme different from the one in Fig 8. It would be clearer for the reader that the topic is different.
Technical corrections:
L. 33: ‘isotope’ instead of ‘isotopic’ analysis
L. 43: ‘isotope’ instead of ‘isotopic’ fractionation
L. 48: ‘isotope’ instead of ‘isotopic’ hydrology
L. 53: ‘sold’ not ‘sell’
L. 64: ‘were creating’ or ‘created’ instead of ‘was creating’
L. 89: ‘2.1’
L. 129: ‘2.2’
L. 135: ‘2.3’
L. 191: please insert ‘measurements’ after ‘water isotope‘
L. 206, 211, 215: ‘dip-in’ instead of ‘Dip-in’, in order to be consistent
L. 218 and 219: please insert ‘data’ or ‘values’ after ‘d-excess’
L. 252-253: ‘isotope’ instead of ‘isotopic’ valuesCitation: https://doi.org/10.5194/egusphere-2025-272-RC3
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