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Figure 5.3: Line profiles ofLiFePO4nanoplates: a) line profile crossing the border of two different chemical phases, that showed 30.2 nm for ptychography and 59.7 nm for STXM image; b) line profile over morphological border with 15.9 nm and 43.0 nm step widths for ptychography and STXM, respectively. The step width was determined as a distance from 10%to 90%of intensity.

of about 23-50 nm in thickness is visible on the right edge of the nanoplate and reveals unreacted region below.

Resolution evaluation was done by measuring width of the step of the line profile going over the morphological edge of the particle from the substrate. Ptychography and STXM showed 15.9 nm and 43.0 nm step width, respectively, that corresponds to more then 2.7 times resolution improvement (figure 5.3 b). Therefore the half pitch resolution of ptychographic images is around 8 nm.

Pre-edge images were taken initially in order to get pure chemical contrast of the lithiated and delithiated regions by subtracting them from on-edge images. However pre-edge images were significantly blurred with some artifacts pronounced on the pre-edges of the nanoplates. The observed artifacts are caused by the reduction of atomic scattering in the pre-edge region, where scattering factorf2has value close to zero andf1is negative.

At the same time the presence of high scattering from morphological features, i.e. edges, produces disconformity of the scattering signal causing the problems in image reconstruc-tion.

and inorganic processes, as well as a combination of both, have been suggested.

The main chemical components of varnish are poorly crystallized Mn oxides, which are incorporated with layers of Fe oxides and clay minerals. Presumably the clay mineral fraction in varnish is formed by the atmospheric dust deposition. However the origin and precipitation of Mn are not yet fully understood. To conceive the genesis of varnish layer is of particular interest for specimens from arid deserts, because it would allow the study of climate changes on the timescale of the whole history of Earth. Therefore a specimen, labeled as CA14 JC-8, collected in Johnson Canyon of Death Valley (California, USA) was investigated using ptychographic imaging2.

Figure 5.4: Preparation of the CA14 JC-8 rock varnish sample: a) cut of slice 0.5 cm thick made perpendicular to the varnish coating, b) example of a micro-basin chosen for FIB preparation, c) SEM image of FIB slice of the varnish sample.

Rock varnish has dense fine-grained layers and is formed on the atmosphere facing side. The side contacting with the soil was covered by an orange-red coating. Since the sample was taken from the ground a few to tens of centimeters of the sample consist of pebbles and small rocks which directly contacted with soil. In order to prepare thin slices for soft X-ray imaging and spectroscopy in transmission the sample was milled by FIB (Ga+ ion beam) to sizes of about 50×30 µm and thicknesses of about 100-200 nm. The region containing thicker varnish, so called micro-basin that is a small depression on horizontal rock surfaces, was chosen for the cut and located by scanning electron microscopy (SEM) (figure 5.4 c). The main challenge in the sample slicing for

2The rock-varnish sample was provided by the Biogeochemistry Department, Max Planck Institute for Chem-istry (Mainz, Germany).

STXM imaging was to cut the varnish strictly perpendicular to the direction of the layered structure. Even in case of insignificant inclination of the layers in respect to the X-ray beam direction the spectroscopic signal will not reveal the layers with different chemical compounds.

Previous study with conventional STXM presented in [114, 115] showed the presence of certain elements of interest, i.e. Fe, Mn, Ca, and C. The distribution of these elements in the sample has been recorded as images at discrete energies and combined in elemental maps. In this work we concentrate on the Mn and Fe content, because layers of these elements might reflect paleoclimate fluctuations. The main assumption is that Mn- layers represent wet climates and Fe rich layers dry climates [116].

Figure 5.5: Element distribution maps obtained by scanning transmission X-ray microscopy: a) overview image of Mn map with white frame showing the region chosen for higher resolution imag-ing and presented on b) and c) ; b) Mn map; c) Fe map [114].

A femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs

LA-ICP-MS) with a spatial resolution of 10-40µmfor the sample CA14 JC-8 is presented in paper [115] and provides determination of major, and in particular, trace element con-centrations. Typically in the area close to the underlying rock Fe abundance is about 20%

higher then Mn concentration. Closer to the varnish surface, theFe2O3amount rises to 50%and theMnO2concentration increases significantly to 25%. At the outer rim of the varnish, MnO2 andFe2O3 have approximately the same abundance, with high Fe2O3

andMnO2concentrations of up to 50%. The region in the middle of the varnish sample (around 12µm from the rim) displaying high amount of Mn (figure 5.5, a) was chosen for STXM element maps. The resolution of STXM images is 35 nm. Figure 5.5 b) and c) show alternating Mn- and Fe-rich layers, continuous and parallel to the host rock surface.

From the Mn map we see that sample has 100-500 nm thick Mn-rich and Mn-poor lay-ers. Fe map has a similar layered pattern but with additional more compact grains of few hundred nanometers in size. These grains refer to morphology of the varnish itself that showed the presence of cavities, which are homogeneously distributed inside the varnish.

Fe-containing minerals were mapped in some of these cavities.

The presence of Mn can be explained by two mechanisms, abiotic and biotic, which both can be involved in Mn layer formation. The first suggestion is an abiotic mecha-nism, when Mn oxides are formed by chemical reduction and precipitation in rainwater with aciditypH≈5.7and reduction potentialEh≈0.8[117]. The second variant is a bi-otic mechanism when Mn reduction occurs due to biological realization by Mn reducing bacteria [118].

The presence of different oxides of Mn is a sign of the formation of different mineral phases or mineral compositions from the beginning of the varnish precipitation. Also they could appear as a result of redox reactions of thinner layers which had the same oxidation state in the beginning. In case of abiotic formation mechanism the presence of different phases can be explained by oxidation process from Mn2+ toMn4+. This process happens in two steps: initially Mn precipitates as an oxyhydroxide (MnOOH) that secondly formsMn4+oxides, e.g. MnO2. PureMn3+minerals are unusual and mostly known as transition oxidation state.Mn3+oxides can be present as oxyhydroxides which are formed also from oxidation ofMn2+ in the presence of abundant Fe oxyhydroxides, which are found in varnish.

Ptychography at rock varnish

The main goal of a ptychographic study is to investigate different oxidation states in var-nish samples that could potentially explain the formation mechanism of Mn layers. Nat-urally varnish has Mn of 2+, 3+, 4+ oxidation states. The X-ray absorption spectrum in figure 5.6 g) shows all three of them in the sample CA14 JC-8. Usually different oxides of Mn do not produce pure phases, instead they exist in a mix with other oxides in various ratios.

Ptychographic images were done with CCD camera placed downstream of the sample at the distance of 8 cm. The setup results in about 12.5 nm output pixel size at Mn absorp-tionL3-edges of different oxidation states 2+, 3+ and 4+ (642.6 eV, 643.4 eV, 645.8 eV), 11 nm at FeL3-edge (712.6 eV) and 5 nm at Al K-edge (1569 eV). Diffraction images at each scanning point were dynamically stacked for 100 ms. The strong scattering on the edges of layered structure provided high photon count rate at the high diffraction orders.

The chemical distributions of three oxidesMn4+,Mn3+ andMn2+ are imaged in figure 5.6 a), b), c), and the image e) is an overlay ofMn2+andMn4+. The ptychographic views on desert varnish sample showed that it has much finer structure that it was found in previous STXM studies. Few hundreds nm thick layers of Mn, which were observed on STXM images, exhibit thinner layers with thicknesses in a range of 18-20 nm, that is in agreement with a previously conducted energy filtered transmission electron microscopy (EFTEM) study which found layers of <20 nm [119].

Some layers posses much higher percentage of only one oxide, other areas have in-termixed state without noticeable domination of one chemical phase over others. As it is seen on theMn4+andMn3+maps they have similar elemental distribution, that means these two oxides are incorporated in the same layers. Mn2+ map has significantly dif-ferent pattern, that has less fine structures and distributed more homogenous over all the imaged area. It means thatMnO2minerals do not, or only in very small quantities, contain Mn2+. The alternating layering of these oxides is the most visible close to the cavities.

The alternating oxidation states of the individual Mn-rich layers contradict the idea of a simple leaching and re-precipitation process of layers along a sedimentary lamination, subsequent to a biogenic precipitation of concentric shells.

The ptychographic image in figure 5.6 f) shows overlay ofMn4+ andFe3+ maps.

Alike STXM images theFe3+map obtained with ptychography shows layered structure, which has wider layers in comparison with theMn4+map, and more compact inclusions evenly distributed in varnish. The layers of Fe belongs to the matrix which crystallized in-situ. The bigger visible spots of Fe on the images are Fe-rich dust grains, which were incorporated in the Mn- and Fe-rich layers from the precipitated mineral dust. Since Mn and Fe behave quite similar, they could be both included in the same mineral. Usually, Fe oxyhydroxides either incorporate Mn in the lattice structure by substitution, or they just absorb Mn from the sedimentary minerals.

Clay minerals, which comprise the bulk of the rock varnish (50-70%), are composed of Mg-Al-Si oxides and cemented by Fe-Mn layers. Therefore Al-rich silicate mineral is distributed fairly homogeneously in rock varnish. Aluminum absorptionK1edge has a peak at 1559.6 eV that results in 5 nm pixel size of the reconstructed ptychography image.

Figure 5.7 shows the amplitude reconstruction with about 10 nm thin layering of Al. Such thin layering in varnish would not be resolved by normal STXM imaging. Aluminum fine layering confirms the sedimentary genesis of the rock varnish coatings.

Taking into account the general growth rate of rock varnish of 1-40µm per 1000 years

Figure 5.6: Element distribution in varnish sample CA14 JC-8 imaged by ptychography: a)Mn4+

map; b)Mn3+map; c)Mn2+map; d)Fe3+map; e) overlay of oxide maps ofMn4+andMn2+; f) overlay ofMn4+andFe3+; g) absorption spectrum of Mn.

[120] with layers representing a continuous environmental record of surrounding area [121] time span of separate layers are assumed to be in a range of 0.5-18 years. This pro-vides a paleoclimate record with a high temporal resolution which can be compared with

Figure 5.7: a) Al map of varnish sample obtained by ptychography with 5 nm pixel size; b) mag-nification of the area from the image a); c) profile along the red line in image b) fitted with double Gauss curve. FWHM of the peak on the line profile showed that layers have around 10.2 nm in thickness.

such paleoclimate records as speleothems, lake sediments, tree rings, or ice core records, which result in annual or even seasonal temporal resolution [122]. However the unique in-formation for desert environment obtained from varnish by high resolution ptychographic studies can not be found in none of the above materials. Sub-10 nm ptychographic res-olution is able to provide insight into the analysis of these samples to track paleoclimate changes with high temporal resolution.

5.3 Magnetic ptychography at domain labyrinth