1 Effects of formation of Aggregate Oil -

2 Suspended Particulate Matter (OSA) in

3 dispersion and degradation of oil in model
4 simulation of dissipative beaches
5 Carine S. Silvaa*, Olivia M. C. de Oliveiraa, b, Icaro T. A. Moreiraa, Antonio F. S. Queiroza, Marcos
6 de Almeidaa, Jéssica V. L. da Silvaa, Igor Oliveira da Silva Andradea

7
a
8 Núcleo de Estudos Ambientais, Instituto de Geociências, Universidade Federal da Bahia,
9 Campus de Ondina, 40170-290, Salvador-BA, Brasil.
b
10 Instituto de Geociências, Departamento de Geofísica, Universidade Federal da Bahia, Campus
11 de Ondina, 40170-290, Salvador-BA, Brasil.

12 *Corresponding author: Tel: +55 71 3283 8632, Fax: + 55 71 3283-8632, Emails address:
13 carine.sntn@gmail.com; santanacarine@hotmail.com.br (Carine Santana Silva)

14

15
16
17 1 INTRODUCTION
18
19
20 The consequences of oil spills are intensified when spills reach
21 the coastline and can affect important ecosystems. Within this context, sandy
22 beaches are environments of considerable socioeconomic and environmental
23 relevance (HOEFEL, 1998) that are commonly associated with oil impact. As a
24 result there is a need to develop countermeasures to oil spills in these
25 environments (NOAA, 1999). The fate of the oil and the magnitude of the impact
26 on the beach can be controlled by several factors: the wave action that influences
27 the residence time of the oil; beach slope, because it determines the deposition
28 area for oil; type of beach substrate, ie, its mineralogical composition, grain size,
29 degree of sphericity and selection, influencing the penetration ability and
30 permanence of oil; the state of the tide; sensitivity of biota on the beach. In
31 addition, the beach may have a natural cycle of accretion / erosion of sediment
32 allowing availability after burial and oil, respectively (ITOPF, 2011).
33 Some methods of cleaning and remediation spills on beaches are
34 traditionally used, the main being the use of absorbent material,
35 manual/mechanical removal, vacuum pumping, blasting water and monitored
36 natural attenuation (API, 1985; ITOPF 2011). However, commonly involve
37 laborious logistical and/or secondary biological effects such as removal of the top
38 layer of sand and trampling the region increasing penetration of the oil
39 (FRICKE et al, 1981; OWENS, 1999; ITOPF 2011).
40 As a result, research on alternative methods based on natural weathering
41 processes of oil are constantly expanding (HOLY, HOLY, 2000; OWENS et al,
42 2003; LI et al, 2008; MOREIRA et al, 2011; MOREIRA et al. 2013). One of these
43 aspects is based on clustering oil - suspended particulate matter (OSA). OSA is
44 a microscopic structure stable for weeks, formed from a natural process where
45 oil droplets and suspended particles interact in a turbulent aqueous medium (LE
46 FLOCH et al, 2002; STOFFYN-EGLI; Lee, 2002.). In this sense, LI et al (2007)
47 conducted a study in wave tank to investigate the effects of fine sediments and
48 chemicals on the dispersion of oil and formation of OSA in seawater dispersants.
49 The results indicated that fine sediment and chemical dispersant, alone
50 or in combination, increased oil dispersion in the water column. It is
51 noteworthy, however, that the use of chemical dispersants is indicated only in
52 the open ocean, far from shore, due to toxic side effects. Oil exploration in
53 coastal waters, however, reflects a need for new strategies for these
54 environments.
55 As an alternative method for accelerating the process of dispersion and
56 degradation of the oil, the surf washing technique, in which the contaminated
57 sediment is relocated to the intertidal zone allowing greater interaction with the
58 waves, was tested on some beaches (LUNEL et al, 1996; GUENETTE et al,
59 2003; OWENS, LEE 2003; SERGY et al, 2003). In fact, the remobilization of
60 sediment intertidal zone to promote increased interaction of oil with suspended
61 particulate matter (SPM) and the abrasion of the waves effectively increases
62 the dispersion of the oil. However, the interaction potential oil-MPS on beaches
63 is reduced by local sedimentary characteristics: mineralogy, grain size high and
64 low in organic matter. Recently, SORENSEN et al., 2014, investigated the
65 interaction of oil droplets dispersed in sea water with sediments of different grain
66 sizes and showed that the formation of OSA is greater with fine sediments.
67 Aggregation with sediments with high granularity, typically found on
68 sandy beaches, occur with greater intensity only in the presence of oils with
 69 higher concentrations of asphaltenes. Clearly see the potential of using fine
70 sediment dispersal and degradation of spilled oil in the coastal zone. Using a
71 mathematical model BANDARA et al. 2011 showed that more than 80% of an
72 oil spill can interact with the suspended particulate matter, and that this total up
73 to 65% of the oil can be removed from the water column by aggregation.
74 Thus, in the event that fine sediment has a tendency to suffer offshore
75 transport, the use of fine sediment (clay + silt) promoting increased interaction
76 oil - MPS can be used to increase the dispersion and degradation of the oil in
77 these environments.
78 This study investigated through subsidiaries in a mesoscale simulation
79 conditions: i) the effects of sediment dispersion in oil, ii) quantify the impact of
80 OSA formation in oil degradation and iii) the potential use of fine sediments in
81 the recovery dissipative beaches impacted by oil.
82

83

84 2 MATERIALS AND METHODS

85

86 2.1 Collection and characterization of sediments

87

88 The sandy sediments used in the simulation model dissipative beaches

89 were collected from the intertidal zone of Itapororoca beach, adjacent to the
90 estuary of the Una, Bahia, Brazil (Fig. 1) river. This is a region where recently
91 the National Agency of Petroleum Natural Gas and Biofuels granted the release
92 of exploration blocks (ANP, 2005), implying a potential impact to the area.
93 The morphodynamic characterization of Itapororoca beach, made from
94 the parameters described in Table 1, allowed to classify it according to the
95 model proposed by WRIGHT and SHORT (1984) as a dissipative beach
96 schema. Thus, it was possible to establish a correlation between the sediment
97 and used to model proposed morphodynamic stage.
98 To accelerate the training of OSA surface sediments were collected at
99 six points along the mangrove estuary of the Una, Bahia, Brazil (Fig. 1) river.
100 This is an environment of low power and predominance of sediment deposition
101 reduced and high concentration of organic matter particle size. Analysis of
102 geochemical characteristics presented in Table 2 and discussed in topic 3.1
103 showed a high potential for aggregation.
104

105 Figure 1. Map location of collection areas in the regions adjacent to the beach and
106 mangrove estuaries of the river Una in the homonymous municipality, southern coast
107 of Bahia, Brazil
108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123 In both cases, the samples were gently collected during the off from the
124 surface of the sediment (0-10cm) with a sampler transferred to stainless steel
125 and aluminum containers previously decontaminated water. Samples were
126 transported immediately to the laboratory and then stored in a freezer (-20 ° C)
127 according to the protocol for the conservation of sediment samples (ASTM
128 D3694-2011). Subsequently they were lyophilized and homogenized for 72
129 hours to ensure uniformity. Only samples from the mangrove sediments were
130 sieved through a 230mesh sieve mesh to select only the clay and silt, since this
131 is the size range most commonly associated with the formation of OSA
132 (BRAGG; OWENS, 1994; SUN, ZHENG, 2009). All sediment samples were
133 sent for analysis of selected physical and chemical properties (Table 2).
134

135 Table 1. Characterization of the beach in the town of Una, Bahia, Brazil, sediment
136 source used in the simulation model dissipative beaches

137
Estation Una
138
15° 15' 01'' S
139 Geographic coordinates 38° 59' 38'' W
Hb (m) 1,8
140
T (s) 9
141
β (°) 3
142 Ws 0,0273
Surf sliding
143
% Coarse Sand 1,8
144
% Media Sand 3,3
145 %Fine Sand 84,2
% Silt 10,6
146 % Clay 0,08

147 Ω 7

148
Stage Morphodynamic Dissipative
149
150 Hb: wave height before breaking; T: wave period; β: slope of the beach face; Ws:
151 Speed settling sediment; Ω: dimensionless parameter DEAN (1973)
152

153

154 The content of organic matter in the sediment was assessed using a
155 method of potassium dichromate (EMBRAPA, 2009). Available phosphorus was
156 extracted by the method described by EMBRAPA (2009) and analyzed by
157 molecular spectrometry. The particle size distribution was determined after
158 removal of organic matter with 30% H2O2, according to the method of FOLK
159 and WARD (1957) using particle analyzer with laser diffraction CILAS 1064.
160

161

162

163
164 2.2 Treatment of fine sediment (silt + clay)
165

166 The sediment used to increase rates of aggregation were collected in the
167 mangrove estuary of Una, Bahia, Brazil river. The sediment was dried by
168 lyophilisation and the 230mesh screened with the aim of selecting sediment
169 particle size range in clay and silt. Studies suggest that the dispersion of the
170 stain is most effective when the application of the sediment is performed using
171 a concentrated solution of sediment (CLOUTIER et al., 2005). Therefore, a
172 solution was prepared at a concentration of 10 g/L in fine sediments and sea
173 water used in the simulation units. As a result a ratio of 1:1 for oil sediment was
174 obtained. This value was selected based on previous studies have shown that
175 the formation of OSA reaches its maximum when the proportion of oil to sludge
176 efficiency is close to unity (KHELIFA et al. 2002, 2005).
177

178

179 2.3 Simulation of beach dissipative

180

181 The dynamics of the dissipative beach environment was simulated by a

182 controlled waves acting within a specific morphology, sediments collected from
183 a dissipative beach and natural seawater system. This study was conducted at
184 the Laboratory for the Study of Oil - LEPETRO on the Federal University of
185 Bahia. The mesoscale experiment was used to evaluate the effects of addition
186 of fine sediments (clay + silt) in an oil spill in dissipative sandy beaches. Four
187 simulation units were built in glass tanks (150X50X50cm). The morphology
188 of shore dissipative by simulating an area with a sand bench and a trough was
189 obtained by a mobile structure (Fig. 2). The background of the simulation units
190 were filled with sediment from the beach Itapororoca in Una station. Controlled
191 waves were created using a high-power pump, allowing for dilution and
192 transport of dispersed oil.
193

194

195
196 Figure 2. Colleges simulation dissipative beaches

197

198

199

200

201

202

203

204

205

206 2.4 Experimental design

207

208 Two experiments were conducted separately: i) the absence of fine

209 sediments (clay + silt) , which formed the OSA was the result of the interaction
210 oil - sandy beach sediments, being called Simulation 1 and ii the presence of
211 fine sediments (clay + silt) with the aim to accelerate the formation of OSA
212 (Simulation 2). For each experiment three replicates and a control experiment,
213 where no sediment was added were performed. About 100g of crude oil was
214 carefully poured over the surface of the sea water in the center of each unit
215 simulation synchronously. The oil tested was obtained from the production of
216 Reconcavo Basin, Bahia, Brazil. This consists of a light, paraffinic oil with an
217 API level 40 and a low percentage of degradation (Figure 3, Table 2). In the
218 second simulation, approximately 10 minutes after pouring the suspension of
219 artificial fine sediments in each simulation unit (or only seawater to the control
220 unit) has been applied. A suspension of 100g/L was sprayed three times over
221 the butch through portable blaster pressure.
222

223

224

225

226
227 Figure 3. Distribution pattern of hydrocarbons from oil Reconcavo Basin analyzed by
228 GC- FID
229

230
231

232

233 In both simulations, samples were collected in a time series of 0, 3, 7, 14

234 and 21 days after the start of the experiment. Composite water samples
235 (600mL) were collected at two locations along the water column: about 5cm
236 below the surface and 5 cm above the bottom in order to assess variations
237 vertical transport of OSA in the water column. Water samples were analyzed
238 by Gas Chromatography with Flame Ionization Detector (GC-FID) to quantify
239 the oil that was dissolved and the fraction that was associated with MPS. The
240 analysis of OSA in microscopy was also performed from temporal samples (5
241 mL) at both depths in order to assess their buoyancy. At the end of the
242 experiment samples of oil and bottom sediment were collected starting time and
243 to estimate the extent of degradation of the oil.
244

245

246

247

248
249 Table 2. Physico-chemical characterization of oil from the Reconcavo Basin used in
250 the simulations
251

252

253

254 2.5 OSA training by ultraviolet fluorescence spectroscopy

255

256 Samples of 5ml were collected for observation and quantification of OSA
257 formed throughout the experiment by transmitted light and epifluorescence
258 ultraviolet illumination (excitation filter 340-390nm; reflection short pass filter
259 400nm; suppression pass filter 430nm) (KEPKAY et al 2002) sing an Olympus
260 inverted microscope model CKX41. Photos of OSA with 10x magnification were
261 recorded from a digital camera attached to the microscope Olympus DP70. The
262 images were processed using Image-Pro ® 6.3 software.
263

264

265 2.6 Dispersion of oil and the formation of OSA in GC - FID

266

267 The samples were processed according to the method described by Li et

268 al 2007. Samples (600mL) collected from amber glass bottles in simulation units
269 were filtered through filters of micro glass fiber (0.5mm) in order to separate the
270 dissolved/colloidal phases and MPS. The filtrate was transferred to a separatory
271 funnel for extraction of hydrocarbons with dichloromethane (DCM) soxhlet
272 extraction with dichloromethane (USEPA method 3540 C). The extracts from
273 both phases were concentrated to 1mL and analyzed by gas chromatography
274 with flame ionization detection (GC-FID) to quantify total petroleum
275 hydrocarbons (TPH) in the filtered phase (HTP mg per liter of water simulation
276 unit) and the particulate phase (HTP mg per gram of solids). The HTPs were
277 quantified using a gas chromatograph Varian CP 3800 equipped with a DB- 5
278 capillary column (30m length, 0.25mm ID, film thickness 0.25lm) and flame
279 ionization detector (FID). The chromatographic conditions are: injector 300°C,
280 initial oven temperature 40°C (2 minutes) at a ramp of 10 ° C min -1 to 300°C
281 temperature for 12 minutes. Helium is used as carrier gas at a flow rate of 1.0ml
282 min-1 and a split ratio of 10:1. A standard solution was prepared from the same
283 TPH (C10-C40) (ASTM D2887 and D6352). As regards the analytical quality
284 control and quantification of the analyte concentration values of the target
285 compounds was in the range of 95% of the reference value assigned to the
286 concentrations of selected hydrocarbons. The accuracy of the measurements
287 obtained by means of repetitions was less than 10% for all target compounds.
288

289 2.7Statistical analyses

290

291 For analysis and description of the sample data descriptive statistics were
292 performed to identify outliers and subsequently the Kolmogorov test was
293 performed - Smirnov test to verify the normality of the data for the concentration
294 of HTP; by chi-square test indicated no significant difference between the
295 variances of the samples. When the variance was homogeneous, ANOVA was
296 applied to a single parametric classification, which showed significant
297 differences between simulations. Principal Component Analysis, Hierarchical
298 Cluster Analysis and Pearson's correlation: Finally, multivariate statistical tests
299 were performed. The analyzes were performed using STATISTICA 9.0 ®
300 software (STATSOFT 2009).
301

302

303

304

305

306
307 3 RESULTS AND DISCUSSION
308

309 3.1 Properties of sediments

310

311 The geochemical characteristics of the sediments used in the simulations

312 are presented in Table 2. Sediment beach was solely responsible for
313 aggregation in simulation 1, comprising about 80% of fine sand. It is noteworthy,
314 however, that despite the relatively large particle size, the sediment is used
315 MPS certainly can be suspended in the water column in coastal environments
316 as a high-energy dissipative beaches. Moreover, due to their size, such particles
317 can provide a fast transfer route of the oil droplets for the bottom sediment.
318 MUSCHENHEIM and LEE (2002) for a review attributed to sorption
319 capacity of hydrophobic compounds not the particle size but the pellets of the
320 organic coating. The content of organic matter associated with the sandy
321 sediment is low, representing only 0.1%. SORENSEN et al., 2014 and an
322 analysis of the influence of physical parameters and chemical dispersants found
323 that carbonate sands and quartz of the same size fraction show similar levels
324 of aggregation. This suggests that the grain size is a dominant factor in
325 controlling the adsorption of oil to the MPS and the mineralogical composition
326 can play in this case secondary.
327 Already GUYOMARCH et al, 2000, suggest that the formation of
328 aggregates of oil - SPM is driven by interactions between polar compounds in
329 oil and negatively charged particles, especially clay. The sediment used to
330 increase the potential for aggregation about 6% of the grains are in the clay size
331 fraction and the rest are distributed in the silt fraction. This pellet also contains
332 about 10% organic matter (Table 2).
333 In a comparative analysis with the sediments in the clay and silt, oil
334 adsorption by sand may be limited by three factors: i) lower amount of
335 suspended sediment since it requires a greater hydrodynamics, ii) by grain size
336 that is associated with a reduced surface area per unit mass percent and less
337 iii) organic matter.
338
339 Table 2. Physical and chemical properties of the sediments used in the simulations

340

341

342

343

344

345

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347

348

349

350

351

352

353

354 3.2 Distribution of units in particle simulation

355

356 The dynamics of the distribution of the particles in the presence and
357 absence of fine sediment (clay + silt) and depth in the subsurface is shown in
358 Figure 4 through the time series of concentration of particulate material in
359 suspension. The total concentrations of particles at the initial time in the
360 absence of fine sediments, averaged 198.42 mg / L in surface. In the second
361 simulation, where silt was added to MPS average surface reaches values of the
362 order of 394.35mg/L. BOEHM (1987) estimated a concentration of MPS in the
363 water column between 10-100mg/L as necessary for adsorption of oil droplet
364 particles in suspension can be an effective mechanism for dispersion. Thus, the
365 initial load conditions MPS, in the absence or presence of fine sediments (clay
366 + silt) there are conditions for an efficient formation of OSA.
367 In the absence of fine sediments, concentrations of suspended
368 particulate matter in the subsurface depth are initially proportional. From the
369 third day there is a significant reduction in the value of MPS in the subsurface,
370 suggesting that concentrations were not initially registered product
371 resuspension by wave action generated. Gradually the proportion of MPS in the
372 background becomes higher, indicating a transfer of the material for this region.
373 This process is greater from the 7th day, i.e., after the aggregation. The
374 association of oil with the sediment changed its density, forming OSAs with low
375 buoyancy. This process occurred in both simulations indicate that the type and
376 concentration of the sediments were not the main driving force of buoyancy.
377 In simulation 2, with the addition of fine sediment concentration of MPS
378 is much higher than just the first day, after the third day the levels stabilize, the
379 next being the background concentrations slightly higher than that found in
380 surface. The influence of the type of sediment in the dispersed oil adsorption
381 was evaluated in figure 5. Was observed that the type of influence MPS oil
382 adsorption. The individual fine particles in the pellet have a higher surface area
383 to adsorb the oil. Moreover, the presence of organic matter associated with this
384 sediment appears to be an important factor in adsorption. The fine sediments
385 absorb oil up to five times from the column with water, the sand used in this
386 study.
387 The interaction between droplets in crude oil and sediment of different
388 particle sizes previously been studied in detail and considering the same
389 concentration of sediments and various size fractions, the amount of oil retained
390 in the aggregate decreases as the grain size (AJIJOLAIYA al., 2006). The
391 presence of organic matter involving the sediment can be a key factor in the
392 aggregation. Studies have shown that sand adsorption capacity of waste oil and
393 the adsorption coefficient differences between silt and clay were seen as
394 dependent on the organic content of the pellet (HARGRAVE and KRANCK,
395 1976; KARICKHOFF et al, 1979).
396

397

398

399

400

401
402 Figure 4. Temporal distribution of suspended particulate matter in the presence and
403 absence of fine sediments (clay + silt)
404

405

406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425 The blue line represents the minimum value considered optimal for formation of OSA.
426

427

428 Figure 5. Variation of the oil capture (mg) depending on the type of sediment. (n = 4)

429

430

431

432

433

434

435

436

437
438 3.3 Distribution of OSA and oil in water column

439 Comments on the stabilization of oil droplets in the water column through the

440 formation of aggregates of oil with the particulate material suspended sediment have

441 been well described in the literature (LEE; STOFFYN - EGLI., 2001; LE FLOCH et al ,

442 2002; OMOTOSO et al, 2002 , Lee et al , 2003; SUN ; ZHENG , 2009; NIU et al , 2010;

443 . SORENSEN et al., 2014). However, in the context of oil spill response operations, there

444 is little information on the fate of OSA formed. In this context, the interactions of the

445 dispersed oil with suspended sediments must also be understood to accurately assess

446 the risks involved during application of fine sediments in the environment.

447 The distribution of oil as a result of dispersion in units of simulation beaches in

448 the presence and absence of fine sediments (clay + silt) was quantified with the analysis

449 of total petroleum hydrocarbons from composite samples collected in the subsurface and

450 at depth. The concentrations of the dissolved HTP and aggregated phases (OSA) were

451 plotted as a function of depth and time in Figures 6 and 7, respectively.

452 In both simulations HTP concentrations associated with MPS is significantly

453 higher than that found in the dissolved phase (p < 0.05). The concentrations of the

454 dissolved phase associated HTP is due to dissolution of the lightest compounds in

455 seawater (Payne et al. 2003). In both simulations the values are higher in the surface

456 than in depth.

457 It appears that the presence of fine sediment (clay + silt) increased significantly

458 (p <0.05) concentration of the particulate HTP (Fig. 7). GUYOMARCH., et al. 2002

459 suggests that the formation of the OSA is the result of interactions of polar compounds

460 in oil , particularly asphaltene content , and the clay particles negatively charged . The

461 oil of the Reconcavo basin used in this study shows about 10 % of resins and

462 asphaltenes (Table 3). Added to this factor the fact that after a spill of crude oil at sea,

463 the lighter compounds are degraded due to evaporation and dissolution (especially in

464 high-energy environments) thereby enriching the relative concentration of asphaltenes.

465 Over time, the remaining oil will therefore have a greater propensity to adsorb particles

466 in sedimentary clay (GUYOMARCH et al., 2002) and sand fraction (SORENSEN et al.,

467 2014). This study was a trend of increased sediment adsorption - oil along the time series

468 simulation.

469

470 Figure 6. Temporal analysis of the oil in the dissolved phase (mg per liter of seawater)
471 for simulations 1 (absence of fine sediments) and 2 (presence of fine sediments). The
472 results presented in accordance with the average value (n = 4)

473
Simulação 1
474 Profundidade Superior
1,00

0,80
Óleo dissolvido (µg/L)

475

0,60
476
0,40

477
0,20

478 0,00
0 3 7 14 21
Tempo (dias)
479

Simulação 2
480
Profundidade Superior
1,00
481
0,80
Óleo dissolvido (µg/L)

482
0,60

483 0,40

0,20
484
0,00
0 3 7 14 21
485
Tempo (dias)

486
487 Figure 7. Temporal analysis of the oil in the particulate phase (mg per g of sediment) for
488 the simulations 1 (no fine sediments) and 2 (presence of silt). The results presented in
489 accordance with the average value (n = 4)

490
Simulação 1
491 Profundidade Superior

70000
HTP particulado (µg/g)

492 60000
50000
40000
493
30000
20000
494 10000
0
0 3 7 14 21
495
Tempo (dias)

496

497
Simulação 2
Profundidade Superior

70000 498
HTP particulado (µg/g)

60000
50000 499
40000
30000 500
20000
10000
501
0
0 3 7 14 21
Tempo (dias) 502

503

504 The effect of adding fine sediments in oil dispersion in the water column units

505 simulation can be assessed by the proportions of oil separation between the dissolved

506 phase and aggregated over the simulations (Fig. 7).

507
508 Figure 7. Oil ratio between dissolved and particulate phases in the simulations partition

509
Simulation 1
510
Superior Profundidade

250000
Razão Partição HTP (g/L)

511
200000

512 150000

100000
513
50000

0
514
0 3 7 14 21
Tempo (dias)
515

516 Simulation 2
Superior Profundidade
517 250000
Razão Partição HTP (g/L)

200000
518
150000

519 100000

50000
520
0
0 3 7 14 21
521 Tempo (dias)

522

523 The structure and size of the OSA formed was analyzed using a UV fluorescence

524 microscope. Figure 8 shows the oil droplet with white light alone (Fig. 8A) and under UV

525 light (Fig. 8b). The scattering coefficient of the oil is higher in sea water than in fresh

526 water. This means that the oils tend to spread over into a fine spot more rapidly in

527 seawater. Furthermore, the lower the interfacial tension in seawater suggests that the oil

528 droplets are more stable in seawater (OMATOSO et al. 2002).

529 Figure 8. Observation in fluorescence microscope droplet oil-free sediments, under white
530 and ultraviolet light

531 a) b)

532

533

534

535

536

537 In Figure 9a is possible to observe the interaction between the oil and the sandy

538 sediment in seawater and in Figure 9b response to interaction with fine sediments.

539 Comparing the figures 9a and 9b we can see a significant increase in the concentration

540 of OSA formed, which corroborates the data of gas chromatography, accompanied by a

541 reduction in the size of these aggregates. In general, we can note that after the addition

542 of fine sediments (clay + silt) aggregates formed are smaller than in the absence of fine

543 sediments.

544

545 Figure 9. Observation of a fluorescence microscope Osas formed in a) absence of fine

546 sediments (Simulation 1) and b) the presence of fine sediments

547 b)
a)

548

549

550

551

552
553 Two structure types previously described by EGLI-STOFFYN were observed;

554 Lee, 2002 the aggregate of the droplet, single or multiple type and aggregate type

555 amorphous without a defined outer contour (Fig. 10).

556

557 Figure 10. Examples of OSA observed in the interaction of the oil with the Reconcavo
558 Basin sediments: the oil appears bright (fluorescent) and sedimentary particles are
559 darker. (a) OSA amorphous type, (b) the OSA droplet type

560 a)
a)
561

562

563

564
b) b)
565

566

567

568

569

570 3.3 Evaluation of landfill of oil in bottom sediment

571 Aggregation with sediment can affect the transport and fate of oil in the

572 environment (LEE, 2002., OWENS et al , 2003; BANDARA et al., 2011) . The dispersion

573 of the aggregates can be horizontal, depending on the current and / or vertically, from the

574 water column to the sediment. The vertical transport is not only changed because of

575 changes in density of the aggregate, but also because of the reduction of the total porosity

576 of the sediment due to the presence of the oil (STERLING JR et al. 2004). These changes
577 are reflected in the buoyancy of the OSA which may be positive, negative or neutral in

578 relation to water, so that this property is controlled by the ratio oil / mineral in each

579 individual household and the local hydrodynamics (LEE; STOFFYN - EGLI., 2001) .

580 Although it was found a large concentration of dispersed oil by sediment in the

581 deeper portion of the water column, about 5cm from the bottom, there seems to be a

582 significant transfer of hydrocarbons between compartments, Figure 11 shows the

583 concentrations of HTP in bottom sediments of the simulation units before the oil spill and

584 the end of the simulations. In the absence of fine sediment concentrations in bottom

585 sediment HTP remained relatively constant, averaging 119, 70 ± 31.53 µg/g at baseline

586 and 94.24 ± 61.51 µg/g at the end of the simulation. In the second simulation, where there

587 was addition of the fine sediment (clay + silt), the average concentration of HTP increased

588 from 162 ± 25.40 µg/g at baseline to 207 ± 65.71 71 µg/g at the end of 21 days.

589 Importantly, however, that these increased levels of HTP is not necessarily associated

590 with petroleum origin.

591 Table 3 lists the concentrations of HTPs, the isoprenoids pristane and phytane

592 and pristane / phytane reason. These geochemical indices are important to clarify the

593 origin of the organic matter deposited in the bottom sediments of the simulation units and

594 thus assess whether the increased levels of HTP is related to natural organic matter

595 associated with the deposition of sediment that has not formed or if the OSA there is a

596 transport of oil associated with OSA to substrate. The transfer of HTPs between the

597 water column and bottom sediment in aquatic environments is of great interest during

598 the evaluation of the effects of dispersion of oil spills (STERLING et al., 2003) and

599 evaluation of impacts to benthic environment.

600 Many studies suggest that a high proportion of the isoprenoids pristane and

601 phytane indicates a biogenic source with a large supply of recent organic matter

602 (VOLKMAN et al., 1992; TOLOSA et al., 1996; Readman et al., 2002; SILVA et al., 2013)

603 and the prevalence of phytane indicate the presence of organic matter from petroleum

604 origin.
605 In the first simulation the pristane/phytane ratio values were always less than one,

606 suggesting petrogênico input. It is noteworthy however that the concentrations of

607 phytane were low (Table 3). The presence of this isoprenoid is typically associated with

608 inputs of oil and is rarely related to a biogenic source (VOLKMAN et al 1992). It is also

609 observed that the eigenvalues are low pristane and phytane equivalent to the so that the

610 ratio becomes lower if only by a small input of organic matter associated with the sandy

611 sediment.

612 In the second simulation the initial hydrocarbon concentrations in fine sediment

613 (clay + silt) is composed of organic matter of biogenic origin, likely the product of

614 decomposition of mangrove plants associated with the collection region. There are

615 however, increased levels of HTP on the last day of the experiment, related, in a timely

616 manner with increasing concentrations of phytane, indicating a small transfer of

617 dispersed oil by sediment into the bottom sediment.

618

619 Figure 11. HTP mean concentration (µg/g) in bottom sediment units simulation of
620 dissipative beaches, in the absence (simulation 1) and presence of fine sediments model
621 (simulation 2)

Tempo 0 Tempo 21

300

250

200
HTP (µg/g)

150

100

50

0
Simulação 1 Simulação 2
622

623
624 Table 3. Concentrations of hydrocarbons (µg/g), isoprenoids pristane and phytane (µg/g)
625 and the ratio pristane / phytane certain sediments used in the simulations at baseline
626 (background) and at the end of the simulation

Pristane
Simulação Código HTP P/F
Phytane

Sand T0.1 97,41 0,07 0,15 0,47

background T0.3 142,00 0,18 0,27 0,68

S1. 1 107,65 0,08 0,13 0,60

S1. 2 234,57 0,31 0,40 0,77

S1. 3 88,34 0,00 0,04 0,10

S1. 4 98,48 0,00 0,05 0,09

Simulation 1

S1. 5 61,42 0,03 0,07 0,43

S1. 6 76,73 0,00 0,01 0,07

S1. 7 42,68 0,00 0,00 0,00

S1. 8 44,09 0,01 0,02 0,91

T0.1 183,62 3,11 0,92 3,38

Background

Sedimentos T0.2 134,21 2,20 0,82 2,67

finos
T0.3 169,14 1,94 1,03 1,87

S2. 1 274,82 1,11 1,09 1,01

S2. 2 234,81 1,02 0,92 1,11

Simulation 2

S2. 3 239,15 0,24 0,31 0,75

S2. 4 247,90 0,40 0,39 1,05

 S2. 5 125,79 0,49 0,45 1,09

S2. 6 123,81 0,41 0,41 1,02

627

628 T0: Values of background sediments; S1 - S21: replicas obtained in simulation 1 (no silt)
629 at the end time; S2 - T0: Replicas obtained in simulation 2 (presence of fine sediments)
630 at baseline; S2 - T21: Simulation 2 (presence of fine sediments) at the end of time.
631

632 3.4 Assessment of the deterioration of oil stain

633 A comparison of the mean levels of degradation in the surface oil slick in the

634 absence (simulation 1) and in the presence of fine sediments (simulation 2) is shown in

635 Figure 12. Comparison of the levels of HTPs presented on day 0 compared to Day 21

636 shows that the degradation of the hydrocarbons was slightly more efficient in the

637 presence of fine sediments.9

638 The results of the simulation control units, where no sediment part of the system,

639 denotes that other weathering factors such as evaporation and oxidation participated in

640 the process, but still the formation of OSA may have contributed to the degradation. Still,

641 it should be emphasized that the levels of degradation at the end of the 21 days are

642 lower, 14.1% and 28.1 % for the simulation in the absence and presence of fine

643 sediments, respectively.

644 Some studies indicate that the process of formation of OSA increases the

645 available surface area per volume of oil, making it more accessible to

646 hydrocarbonoclastic bacteria and allowing greater contact with oxygen, thus accelerating

647 the degradation process (Lee et al., 1996 , OWENS , Lee , 2003; WEISE et al , 1999). .

648 Although it has been found an efficient dispersion of the oil from the particulate material

649 in suspension throughout the three weeks of the experiment, the kinetics of degradation

650 of these compounds tends to be slower and thus it is possible that the period of the

651 simulation has been a limiting research.

652 Figure 12. Average degradation HTP (%) from the oil slick on the surface of simulation
653 units 1 and 2 and their corresponding controls

100
90
80
70
60
HTP (%)

50
40
30
20
10
0
S- 00 S1- 21 S2- 21
Unidade de Simulação - Experimento Unidade de Simulação - Controle
654

655 S - 00: Initial concentration of oil in the Reconcavo Basin used in both simulations. S1 -
656 S21: Simulation 1 (no silt) at the end time; S2 - T21: Simulation 2 (presence of fine
657 sediments) at the end of time
658

659 It is possible to make a detailed analysis of the degradation of surface oil from

660 figure 13, where the relative percentage of saturated and aromatic resins and asphaltenes

661 (NSO) fractions was assessed at the end of the experiment the initial time and in the

662 absence (simulation 1) and presence (simulation 2) of fine sediments. It can be seen that

663 there was a 21- time selective removal of saturated compounds and the relative

664 enrichment of aromatic fractions and resins and asphaltenes from the initial oil. The lighter

665 compounds are preferentially lost by evaporation or dissolution in the water column.

666 These results are consistent with the higher solubility of the low molecular weight

667 compounds in the water. In fact, this process confirms the increase in the levels of

668 aggregation in a time series (Fig. 6). The relative enrichment of the heavier oil compounds

669 allow for a pellet adsorption - enhanced oil (GUYOMARCH et al., 2002). This process

670 was verified with greater intensity in the presence of silt, where the formation of OSA was

671 also higher, suggesting a correlation between the level of enrichment of the heavier oil

672 fractions (aromatics and asphaltenes and resins) and the interaction oil - MPS.
673 Figure 13. Middle fractions of saturated compounds, aromatics, resins and asphaltenes
674 (%) from the surface oil slick at time 0 and time 21 in simulations 1 and 2 distribution
675

Óleo - T0

Óleo - T21 (Simulação 1)

Óleo - T21 (Simulação 2)

0 20 40 60 80 100

% NOS % ARO % SAT

676

677 SAT: Saturated; ARO: Aromatic; NSO: Resins and Asphaltenes.

678

679 3.5 Integrated assessment

680 The analysis of how the oil dispersed by the sediment is influenced by the

681 concentrations of organic matter, organic carbon, phosphorus, carbonate and physical-

682 chemical parameters (temperature, pH, salinity and dissolved oxygen) was assessed by

683 Principal Component Analysis (PCA) (Fig. 14). The analysis considered time 0 and time

684 21. The first PC accounted for 56.47 % of total variance and the second accounted for

685 37.20%, totaling about 93 % of the total variance explicability data. A joint interpretation

686 of PCA with Hierarchical Classification Analysis (HCA) (Fig. 3) it is possible to establish

687 a relationship between geochemical parameters and the simulations at each time

688 investigated. Factor 1 is primarily responsible for separating the initial time (S1 - S2 and

689 T0 - T0) and final (S1 - S2 and T21 - T21) of the simulations due to higher levels of

690 hydrocarbons and higher salinity at the end of the experimente. The Factor 2 simulations

691 in the absence and presence of fine sediments where the simulation is associated with

692 the 2 highest concentrations of nutrients.

693 It was also observed from the Pearson correlation (Table 4) a strong positive

694 correlation between salinity, dissolved hydrocarbons with scattered by sediment

695 suggesting that these factors acted in a convergent way for aggregation oxygen. In both

696 simulations there was an increase in the salinity of the time 21 relative to time 0, because

697 the evaporation of seawater. The salinity by interfering ionic strength on the ability of

698 flocculation of the solid particles and also modifies the properties of the oil droplets

699 affecting the rate of formation of OSA (LE FLOCH et al. 2002). In saline water, this

700 process is more efficient because the presence of free ions reduces the electrostatic

701 repulsion force between the sedimentary particles (negatively charged) and enhances

702 molecular attraction force becomes dominant and allows coalescence between the solid

703 particles and polar compounds in oil (SUN; ZHENG, 2009). The increased rate of

704 evaporation of water also suggests a higher evaporation of low molecular weight

705 compounds in the oil and therefore the enrichment of polar compounds also increase the

706 interaction oil - sediment (GUYOMARCH et al, 2002). Negative correlations between

707 temperature and dissolved oxygen were also recorded and reflect the evaporation rates.

708 A strong negative correlation between temperature and the levels of HTP

709 associated with MPS. In fact, the process of dissolving the oil in sea water is most intense

710 at the higher temperature environment. At the time series of simulations was verified a

711 decrease in the temperature of seawater process more evident in the surface layer.

712 Thus, aggregation appears to have a higher response at lower temperatures. Similar

713 results were obtained by SORENSEN et al., 2014.

714

715

716

717

718
719 Figure 14. Analysis and Principal Component Analysis Hierarchical Classification (Factor
720 1 x Factor 2) between the oil associated with OSA and geochemical parameters at time
721 0 and time 21 days for the simulations in the absence and presence of fine sediments
722
4

723
3

S2 - T0
2
724
S2 - T21
1

Factor 2: 37,20%
725
0

S1 - T0
726 -1

-2 S1 - T1

727
-3

728 -4
-5 -4 -3 -2 -1 0 1 2 3 4
Factor 1: 56,47%

729 S1 - T0: Simulation 1 (absence of fine sediments) at baseline; S1 - S21: Simulation 1 (no
730 silt) at the end time; S2 - T0: Simulation 2 (presence of fine sediments) at baseline; S2 -
731 T21: Simulation 2 (presence of fine sediments) at the end of time.
732

733 Table 4. Pearson correlation matrix applied to the formation and dispersal of OSA
734 simulations on models of dissipative beaches
pH T Sal DO HTP Sup HTP Prof MO COT P

pH 1,00

T 0,48 1,00

Sal -0,65 -0,40 1,00

DO -0,46 -0,76 0,85 1,00

HTP Sup -0,69 -0,80 0,87 0,96 1,00

HTP Prof -0,73 -0,78 0,88 0,95 1,00 1,00

MO 0,33 -0,67 -0,06 0,47 0,31 0,27 1,00

 COT 0,33 -0,67 -0,06 0,47 0,31 0,27 1,00 1,00

P 0,43 -0,54 -0,42 0,12 0,01 -0,03 0,92 0,92 1,00

735 Bold values of p <0.05. OM: organic matter; TOC: Total Organic Carbon; P: phosphorus.
736 T: Temperature, Sal: salinity; DO: Dissolved Oxygen; pH: hydrogen potential; Sup HTP:
737 dispersed oil by 5cm below the sediment surface; HTP inf: dispersed oil at 5cm above
738 the sediment surface.

739

740 The pH tended to decrease along the simulations, from basic to neutral at the

741 initial time at the end time. These values are close to the normal range for sea water

742 where the pH varies between 7.8 and 8.2. The observed negative correlation with the

743 concentration of MPS associated HTP, where lowering the pH can be associated with

744 generation of acid byproducts generated during the biodegradation process oil

745 (ANDRADE et al., 2010).

746

747 4. CONCLUSIONS

748

749 Cleaning techniques and remediation traditionally applied beaches are limited.

750 The natural process of dispersion and degradation of the oil slick in these regions

751 involves abrasion by waves and interaction with the MPS forming the OSA. The potential

752 for aggregation of sediment commonly associated with dissipative beaches is limited

753 depending on the particle size and percentage of organic matter.

754 This study aimed to evaluate the effects of using dissipative beaches in fine

755 sediments through mesoscale models in order to disperse the oil, the impact of OSA in

756 the formation of stain and degradation of potential use in the recovery of fine sediments

757 affected dissipative beaches by oil.

758 It was found that interaction oil - MPS was significantly only in the presence of

759 the sandy sediment. In the natural environment, the high energy in the surf zone causes
760 the sandy sediment, despite the high particle size, is suspended in the water column and

761 thus, in case of a spill certainly the natural process of formation of OSA may occur.

762 The results, however, support the hypothesis that the fine sediments have a

763 significant effect on the formation of OSA and accelerating the dispersion of the oil in the

764 water column. In the presence of a dispersion of fine sediment was five times higher

765 compared to the oil in the sandy sediment.

766 In both simulations the OSA was maintained preferably formed on the bottom of the

767 water column, and because of that no significant transfer of petroleum hydrocarbons to

768 the substrate, thereby reducing the potential impact on benthic organisms. Thus, as a

769 measure of dispersion of the oil in the water column is well known that the use of fines

770 to increase the formation of sediments OSA is an efficient measure.

771 In terms of degradation of the oil spot was not observed a significant difference

772 in the absence or presence of fines during the 21 days of simulated sediment. Thus, with

773 respect to its application in remediation processes in dissipative beaches greater time

774 series analysis combined with microbiological evaluation is needed to establish whether

775 in fact the formation of OSA is contributing to the degradation of the oil.

776 The use of fine sandy sediments for the purpose of dispersing the oil beaches

777 should be considered carefully based on local parameters such as MPS, type of oil

778 spilled, temperature, and especially the transport direction of currents, ensuring offshore

779 transport for OSA and of course, predicting the fate of this material.

780

781 ACKNOWLEDGMENTS

782

783 This study was performed with financial support from the CAPES and QUEIROZ

784 GALVÃO EXPLORATION AND PRODUCTION SA.

785
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